Detergent compositions comprising polymeric suds enhancers which have improved mildness and skin feel

ABSTRACT

Compositions comprising one or more polymeric suds volume and suds duration enhances which are mild on the user&#39;s skin. The polymeric suds enhances are suitable for use in methods which in use as compositions light duty liquid, LDL compositions, hand dishwashing compositions, laundry bars, personal cleansing compositions and the like.

RELATED APPLICATIONS

This application is a divisional of prior U.S. application Ser. No.09/979,562, filed on Nov. 14, 2001 now U.S. Pat. No. 6,827,795; whichwas the National Stage of International Application No. PCT/US00/14405,filed May 25, 2000; which claimed the benefit of U.S. ProvisionalApplication No. 60/135,888, filed May 26, 1999.

FIELD OF THE INVENTION

The present invention relates to compositions comprising one or morepolymeric suds volume and suds duration enhances which are mild on theusers skin. The polymeric suds enhances are suitable for use in methodswhich in use as compositions light duty liquid, LDL compositions, handdishwashing compositions, laundry bars, personal cleansing compositionsand the like.

BACKGROUND OF THE INVENTION

In formulating detergent compositions which will foreseeable contact theusers skin, such as Light-duty liquid or gel dishwashing detergentcompositions laundry bars, personal cleansing compositions (such asshampoos and body washes) and the like the problem of mildness is ofmajor concern. Furthermore, the formulator must also produce acomposition which provides adequate cleaning for the desired end use.However, it is well know that the best cleaning surfactants, such as theanionic surfactants, for example LAS, AS etc., irritate the users skin.The alternative has been to use surfactants which do not irritate theuser's skin, however these are typically not the bets cleaningsurfactants available. The formulator is presented with the difficulttask of resolving these two seemingly conflicting, properties.

Consequently, their remains the need for a detergent composition whichcan have the best possible cleaning while being mild enough forprolonged contact with users skin.

SUMMARY OF THE INVENTION

It has now been found that the suds boosting polymers described hereinwhen added to a added to a detergent composition improves the mildnessof the composition, even those compositions containing harshsurfactants, and surprisingly improves skin mildness.

The present invention meets the aforementioned needs in that it has beensurprisingly discovered that certain polymers serve not only as sudsduration and suds volume extenders, but also enhance the mildness of adetergent composition. The effective polymers of the present inventionprovide both increased suds volume and suds duration when formulated ina detergent composition.

A first aspect of the present invention relates to a method for manuallycleaning an object, preferably tableware, such as plates, glasses,flatware etc., fabrics, such as clothing, bed linen, carpets, etc., skinor hair, comprising contacting a user's hands with a washing solutioncomprising water and a detergent composition in which suds produced bythe solution is maintained for an extended period of time by a polymericsuds stabilizer, said suds stabilizer is selected from the groupconsisting of:

-   -   (a) polymers comprising at least one monomeric unit of the        formula:

-   -   wherein each of R¹, R² and R³ are independently selected from        the group consisting of hydrogen, C, to C₆ alkyl, and mixtures        thereof; L is selected from the group consisting of a bond, O,        NR⁶, SR⁷R⁸ and mixtures thereof, wherein R⁶ is selected from the        group consisting of hydrogen, C₁ to C₈ alkyl and mixtures        thereof; each of R⁷ and R⁸ are independently hydrogen, O, C₁ to        C₈ alkyl and mixtures thereof, or SR⁷R⁸ form a heterocyclic ring        containing from 4 to 7 carbon atoms, optionally containing        additional hetero atoms and optionally substituted; Z is        selected from the group consisting of: —(CH₂)—, (CH₂—CH═CH)—,        —(CH₂—CHOH)—, (CH₂—CHNR⁶)—, —(CH₂—CHR¹⁴—O)— and mixtures        thereof; wherein R¹⁴ is selected from the group consisting of        hydrogen, C₁ to C₆ alkyl and mixtures thereof; z is an integer        selected from about 0 to about 12; A is NR⁴R⁵, wherein each of        R⁴ and R⁵ are independently selected from the group consisting        of hydrogen, C₁ to C₈ alkyl, and mixtures thereof, or NR⁴R⁵ form        an heterocyclic ring containing from 4 to 7 carbon atoms,        optionally containing additional hetero atoms, optionally fused        to a benzene ring, and optionally substituted by C₁ to C₈        hydrocarbyl; and wherein said polymeric suds stabilizer has a        molecular weight of from about 1,000 to about 2,000,000 daltons;    -   (b) a proteinaceous suds stabilizer, said proteinaceous suds        stabilizer having an isoelectric point of from about 7 to about        11.5; and    -   (c) a zwitterionic polymeric suds stabilizer;        wherein said method further including the step of washing the        object with said solution; and wherein said suds stabilizer is        a, mild, suds enhancing, suds stabilizer such that a user's        hands, after submersion in a solution containing said suds        stabilizer, are not irritated.

A second aspect of the present invention relates to a method ofenhancing mildness of a detergent composition comprising a surfactantsystem comprising an anionic surfactant or a mixture of anionicsurfactants which method comprises adding a polymeric suds stabilizer tosaid composition, wherein said polymeric suds stabilizer is selectedfrom the group consisting of:

-   -   (a) polymers comprising at least one monomeric unit of the        formula:

-   -   wherein each of R¹, R², R³, L, Z, z and A are as hereinbefore        defined; and wherein said polymeric suds stabilizer has a        molecular weight of from about 1,000 to about 2,000,000 daltons;    -   (b) a proteinaceous suds stabilizer, said proteinaceous suds        stabilizer having an isoelectric point of from about 7 to about        11.5; and    -   (c) a zwitterionic polymeric suds stabilizer;

A third aspect of the present invention relates to a method of cleaningthe skin while avoiding the harsh effects on the skin of an anionicsurfactant by washing the skin with the composition comprising apolymeric suds stabilizer selected from the group consisting of:

-   -   (a) polymers comprising at least one monomeric unit of the        formula:

-   -   wherein each of R¹, R², R³, L, Z, z and A are as hereinbefore        defined; and wherein said polymeric suds stabilizer has a        molecular weight of from about 1,000 to about 2,000,000 daltons;    -   (b) a proteinaceous suds stabilizer, said proteinaceous suds        stabilizer having an isoelectric point of from about 7 to about        11.5; and    -   (c) a zwitterionic polymeric suds stabilizer;

A fourth aspect of the present invention relates to a method formanually cleaning an object comprising contacting a user's hands with awashing solution comprising water and a detergent composition in whichsuds produced by the solution is maintained for an extended period oftime by a suds stabilizer, said suds stabilizer comprising

-   -   i) units capable of having a cationic charge at a pH of from        about 4 to about 12; provided that said suds stabilizer has an        average cationic charge density of at least about 0.01 units per        100 daltons molecular weight at a pH of from about 4 to about        12; and        wherein said method further including the step of washing the        object with said solution; and wherein said suds stabilizer is        a, mild, suds enhancing, suds stabilizer such that a user's        hands, after submersion in a solution containing said suds        stabilizer, are not irritated.

A fifth aspect of the present invention relates to a method of enhancingmildness of a detergent composition comprising a surfactant systemcomprising an anionic surfactant or a mixture of anionic surfactantswhich method comprises adding a polymeric suds stabilizer to saidcomposition, wherein said polymeric suds stabilizer comprising:

-   -   i) units capable of having a cationic charge at a pH of from        about 4 to about 12; provided that said suds stabilizer has an        average cationic charge density of at least about 0.01 units per        100 daltons molecular weight at a pH of from about 4 to about        12;

A sixth aspect of the present invention relates to a method of cleaningthe skin while avoiding the harsh effects on the skin of an anionicsurfactant by washing the skin with the composition comprising aneffective amount of a polymeric suds stabilizer, said polymeric sudsstabilizer comprising:

-   -   i) units capable of having a cationic charge at a pH of from        about 4 to about 12; provided that said suds stabilizer has an        average cationic charge density of at least about 0.01 units per        100 daltons molecular weight at a pH of from about 4 to about        12;

These and other aspects, features and advantages will become apparent tothose of ordinary skill in the art from a reading of the followingdetailed description and the appended claims.

In the description of the invention various embodiments and/orindividual features are disclosed. As will be apparent for the skilledpractitioner all combinations of such embodiments and features arepossible and can result in preferred executions of the invention.

All percentages, ratios and proportions herein are by weight, unlessotherwise specified. All temperatures are in degrees Celsius (° C.)unless otherwise specified. All documents cited are in relevant part,incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to methods which in addition to providingincreased suds volume and increase suds duration, are mild. The methodsof the present invention comprise suds boosting polymers selected from(1) polymers comprising at least one monomeric unit; (2) proteinaceoussuds stabilizer; (3) zwitterionic polymeric suds stabilizer; and (4)polymers comprising units capable of having a cationic charge. Suitablepolymeric suds stabilizers, include be a homopolymers, as well ascopolymers, terpolymers, and higher multimers. Mixtures of the polymericsuds stabilizers are also within the scope of the invention.

In addition, the polymers of the present invention act together withsurfactants and other adjunct ingredients to provide for efficientgrease cutting and anti-redepositon of grease.

It is believed, while not wanting to be limited by theory, that the sudsboosting polymers functions primarily by providing a desquamatory actionto the composition. It is believed that the suds boosting polymersremove damaged (e.g. dry) skin cells on the surface of the skin, therebyreducing the rough feel associated therewith. The suds boosting polymersremoves the effect of prior damage to the skin, giving the skin afresher, more youthful appearance and feel. When the suds boostingpolymers is combined with a detergent surfactant the overall effect isto promote the health of the skin and to provide the consumer with aperceived mildness or skin feel/appearance advantage over other similarcompositions which do not contain the suds boosting polymers while stillmaintaining good cleaning performance.

Alternatively, the polymeric suds stabilizers may, again while notwanting to be limited by theory, just improve the overall feel of thecomposition to the user.

1. Polymers Comprising at Least One Monomeric Unit

In one aspect of the present invention the polymeric suds stabilizerscomprise at least one monomeric unit of the formula:

wherein each of R¹, R² and R³ are independently selected from the groupconsisting of hydrogen, C₁ to C₆ alkyl, and mixtures thereof, preferablyhydrogen, C₁ to C₃ alkyl, more preferably, hydrogen or methyl. L isselected from the group consisting of a bond, O, NR⁶, SR⁷R⁵ and mixturesthereof, preferably, O, NR⁶, wherein R⁶ is selected from the groupconsisting of hydrogen, C₁ to C₈ alkyl and mixtures thereof, preferably,hydrogen, C₁ to C₃, and mixtures thereof, more preferably hydrogen,methyl; each of R⁷ and R⁸ are independently hydrogen, O, C₁ to C₈ alkyland mixtures thereof, preferably, hydrogen, C₁ to C₃, and mixturesthereof, more preferably hydrogen or methyl. By “O”, an oxygen linkedvia a double bond is meant, such as a carbonyl group. Furthermore thismeans that when either or both R⁷R⁸ is “O”, SR⁷R⁸ can have the followingstructures:

Alternatively, SR⁷R⁸ form a heterocyclic ring containing from 4 to 7carbon atoms, optionally containing additional hetero atoms andoptionally substituted. For example SR⁷R⁸ can be:

However, it is preferred that SR⁷R⁸, when present, is not a heterocycle.

When L is a bond it means that there is a direct link, or a bond,between the carbonyl carbon atom to Z, when z is not zero. For example:

When L is a bond and z is zero, it means L is a bond from the carbonylatom to A. For example:

Z is selected from the group consisting of: —(CH₂)—, (CH₂—CH═CH)—,—(CH₂—CHOH)—, (CH₂—CHNR⁶)—, —(CH₂—CHR¹⁴—O)— and mixtures thereof,preferably —(CH₂)—. R¹⁴ is selected from the group consisting ofhydrogen, C₁ to C₆ alkyl and mixtures thereof, preferably hydrogen,methyl, ethyl and mixtures thereof; z is an integer selected from about0 to about 12, preferably about 2 to about 10, more preferably about 2to about 6.

A is NR⁴R⁵. Wherein each of R⁴ and R⁵ are is independently selected fromthe group consisting of hydrogen, C₁–C₈ linear or branched alkyl,alkyleneoxy having the formula:—(R¹⁰O)_(y)R¹¹

wherein R¹⁰ is C₂–C₄ linear or branched alkylene, and mixtures thereof;R¹¹ is hydrogen, C₁–C₄ alkyl, and mixtures thereof; y is from 1 to about10. Preferably R⁴ and R⁵ are independently, hydrogen, C₁ to C₄ alkyl.Alternatively, NR⁴R⁵ can form a heterocyclic ring containing from 4 to 7carbon atoms, optionally containing additional hetero atoms, optionallyfused to a benzene ring, and optionally substituted by C₁ to C₈hydrocarbyl. Examples of suitable heterocycles, both substituted andunsubstituted, are indolyl, isoindolinyl imidazolyl, imidazolinyl,piperidinyl pyrazolyl, pyrazolinyl, pyridinyl, piperazinyl,pyrrolidinyl, pyrrolidinyl, guanidino, amidino, quinidinyl, thiazolinyl,morpholine and mixtures thereof, with morpholino and piperazinyl beingpreferred. Furthermore the polymeric suds stabilizer has a molecularweight of from about 1,000 to about 2,000,000 preferably from about5,000 to about 1,000,000, more preferably from about 10,000 to about750,000, more preferably from about 20,000 to about 500,000, even morepreferably from about 35,000 to about 300,000 daltons. The molecularweight of the polymeric suds boosters, can be determined viaconventional gel permeation chromatography.

While, it is preferred that the polymeric suds stabilizers be selectedfrom homopolymer, copolymers and terpolymers, other polymers (ormultimers) of the at least one monomeric unit, the polymeric sudsstabilizers can also be envisioned via polymerization of the at leastone monomeric unit with a wider selection of monomers.

That is, all the polymeric suds stabilizers, can be a homopolymers,copolymers, terpolymers, etc. of the at least one monomeric unit, or thepolymeric suds stabilizer can be copolymers, terpolymers, etc.containing one, two or more of the at least one monomeric unit and one,two or more monomeric units other than the at least one monomeric unit.For example a suitable homopolymer is:

wherein R¹, R⁴, R⁵ and z are as hereinbefore defined. For example asuitable copolymer is:

-   -   wherein R¹, R⁴, R⁵ and z are as hereinbefore defined; and

-   -   wherein R¹ and L are as hereinbefore defined, and B is selected        from the group consisting of hydrogen, C₁ to C₈ hydrocarbyl,        NR⁴R⁵, and mixtures thereof; wherein each of R⁴ and R⁵ are        independently selected from the group consisting of hydrogen, C₁        to C₈ alkyl, and mixtures thereof, or NR⁴R⁵ form a heterocyclic        ring containing from 4 to 7 carbon atoms, optionally containing        additional hetero atoms, optionally fused to a benzene ring, and        optionally substituted by C₁ to C₈ hydrocarbyl;        wherein ratio of (i) to (ii) is from about 99:1 to about 1:10.        Some preferred examples of

are:

For example a copolymer can be made from two monomers, G and H, suchthat G and H are randomly distributed in the copolymer, such as

-   -   GHGGHGGGGGHHG . . . etc.        or G and H can be in repeating distributions in the copolymer,        for example    -   GHGHGHGHGHGHGH . . . etc.,        -   or    -   GGGGGHHGGGGGHH . . . etc.,

The same is true of the terpolymer, the distribution of the threemonomers can be either random or repeating.

For example a suitable polymeric suds stabilizer, which is a copolymeris:

-   -   wherein R¹, R⁴, R⁵ and z are as hereinbefore defined; and

-   -   wherein R¹ Z and z are as hereinbefore defined, each of R¹² and        R¹³ are independently selected from the group consisting of        hydrogen, C₁ to C₈ alkyl and mixtures thereof, preferably,        hydrogen, C₁ to C₃, and mixtures thereof, more preferably        hydrogen, methyl, or R¹² and R¹³ form a heterocyclic ring        containing from 4 to 7 carbon atoms; and R¹⁵ is selected from        the group consisting of hydrogen, C₁ to C₈ alkyl and mixtures        thereof, preferably, hydrogen, C₁ to C₃, and mixtures thereof,        more preferably hydrogen, methyl,        wherein ratio of (i) to (ii) is from about 99:1 to about 1:10.

Some preferred at least one monomeric units, which can be additionallycombined together to from copolymers and terpolymers include:

An example of a preferred homopolymer is 2-dimethylaminoethylmethacrylate (DMAM) having the formula:

Some preferred copolymers include:

copolymers of

An example of a preferred copolymer is the (DMA)/(DMAM) copolymer havingthe general formula:

wherein the ratio of (DMA) to (DMAM) is about 1 to about 10, preferablyabout 1 to about 5, more preferably about 1 to about 3.

An example of a preferred copolymer is the (DMAM)/(DMA) copolymer havingthe general formula:

wherein the ratio of (DMAM) to (DMA) is about 1 to about 5, preferablyabout 1 to about 3.

These polymeric suds stabilizers when used in the methods of the presentinvention are present at an effective amount of the polymeric sudsstabilizers, (i) described herein, preferably from about 0.01% to about10%, more preferably from about 0.05% to about 5%, most preferably fromabout 0.1% to about 2% by weight, of said composition. What is meantherein by “an effective amount polymeric suds stabilizers” is that thesuds volume and suds duration produced by the presently describedcompositions are sustained for an increased amount of time relative to acomposition which does not comprise one or more of the polymeric sudsstabilizer described herein. Additionally, the polymeric suds stabilizercan be present as the free base or as a salt. Typical counter ionsinclude, citrate, maleate, sulfate, chloride, etc.

These and other suitable polymeric suds stabilizers and methods ofpreparing them, can be found in PCT/US98/24853 filed Nov. 20, 1998.

2 Proteinaceous Suds Stabilizer

The proteinaceous suds stabilizers of the present invention can bepeptides, polypeptides, amino acid containing copolymers, and mixturesthereof. Any suitable amino acid can be used to form the backbone of thepeptides, polypeptides, or amino acid containing copolymers of thepresent invention provided at least 10% to about 40% of said amino acidswhich comprise the peptides are capable of being protonated at a pH offrom 7 to about 11.5.

The proteinaceous suds stabilizers of the present invention comprise atleast about 10% by weight of one or more amino acid residues, preferablyamino acid residues having a proton accepting or proton donor moiety.The proteinaceous suds stabilizers can comprise any other amino acidcompatible units which provide for extended suds formation and sudsvolume.

For the purposes of the present invention the term “peptide” and“polypeptide” stand equally well for polymers which comprise 100% aminoacids as described herein below and which have a molecular weight of atleast about 1500 daltons. For the purposes of the present invention theterm “amino acid containing co-polymers” is defined as “polymericmaterial comprising at least about 10% by weight of one or more aminoacids as defined herein provided said polymeric material has a molecularweight of at least about 1500 daltons”.

The preferred proteinaceous suds stabilizers according to the presentinvention have an isoelectric point of form 7 to about 11.5, preferablyfrom about 8.5 to about 11.5, more preferably form about 9.5 to about11.

In general, the amino acids suitable for use in forming theproteinaceous suds stabilizers of the present invention have from 2 to22 carbon atoms, said amino acids having the formula:

wherein R and R¹ are each independently hydrogen, C₁–C₆ linear orbranched alkyl, C₁–C₆ substituted alkyl, and mixtures thereof.Non-limiting examples of suitable moieties for substitution on the C₁–C₆alkyl units include amino, hydroxy, carboxy, amido, thio, thioalkyl,phenyl, substituted phenyl, wherein said phenyl substitution is hydroxy,halogen, amino, carboxy, amido, and mixtures thereof. Furthernon-limiting examples of suitable moieties for substitution on the R andR¹ C₁–C₆ alkyl units include 3-imidazolyl, 4-imidazolyl, 2-imidazolinyl,4-imidazolinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl,1-pyrazolyl, 3-pyrazoyl, 4-pyrazoyl, 5-pyrazoyl, 1-pyrazolinyl,3-pyrazolinyl, 4-pyrazolinyl, 5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl,4-pyridinyl, piperazinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, guanidino,amidino, and mixtures thereof. Preferably R¹ is hydrogen and at least10% of R units are moieties which are capable of having a positive ornegative charge at a pH of from about 7 to about 11.5. Each R² isindependently hydrogen, hydroxy, amino, guanidino, C₁–C₄ alkyl, orcomprises a carbon chain which can be taken together with R, R¹ any R²units to form an aromatic or non-aromatic ring having from 5 to 10carbon atoms wherein said ring may be a single ring or two fused rings,each ring being aromatic, non-aromatic, or mixtures thereof. When theamino acids according to the present invention comprise one or morerings incorporated into the amino acid backbone, then R, R¹, and one ormore R² units will provide the necessary carbon—carbon bonds toaccommodate the formation of said ring. Preferably when R is hydrogen,R¹ is not hydrogen, and vice versa; preferably at least one R² ishydrogen. The indices x and y are each independently from 0 to 2.

An example of an amino acid according to the present invention whichcontains a ring as part of the amino acid backbone is 2-aminobenzoicacid (anthranilic acid) having the formula:

wherein x is equal to 1, y is equal to 0 and R, R¹, and 2 R² units fromthe same carbon atom are taken together to form a benzene ring.

A further example of an amino acid according to the present inventionwhich contains a ring as part of the amino acid backbone is3-aminobenzoic acid having the formula:

wherein x and y are each equal to 1, R is hydrogen and R¹ and four R²units are taken together to form a benzene ring.

Non-limiting examples of amino acids suitable for use in theproteinaceous suds stabilizers of the present invention wherein at leastone x or y is not equal to 0 include 2-aminobenzoic acid, 3-aminobenzoicacid, 4-aminobenzoic acid, b-alanine, and b-hydroxyaminobutyric acid.

The preferred amino acids suitable for use in the proteinaceous sudsstabilizers of the present invention have the formula:

wherein R and R¹ are independently hydrogen or a moiety as describeherein above preferably R¹ is hydrogen and at least from about ¹⁰% toabout 40% of R units comprise a moiety having a positive charge at a pHof from about 7 to about 11.5.

More preferred amino acids which comprise the proteinaceous sudsstabilizers of the present invention have the formula:

wherein R is hydrogen, C₁–C₆ linear or branched alkyl, C₁–C₆ substitutedalkyl, and mixtures thereof. R is preferably C₁–C₆ substituted alkylwherein preferred moieties which are substituted on said C₁–C₆ alkylunits include amino, hydroxy, carboxy, amido, thio, C₁–C₄ thioalkyl,3-imidazolyl, 4-imidazolyl, 2-imidazolinyl, 4-imidazolinyl,2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1-pyrazolyl, 3-pyrazoyl,4-pyrazoyl, 5-pyrazoyl, 1-pyrazolinyl, 3-pyrazolinyl, 4-pyrazolinyl,5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, piperazinyl,2-pyrrolidinyl, 3-pyrrolidinyl, guanidino, amidino, phenyl, substitutedphenyl, wherein said phenyl substitution is hydroxy, halogen, amino,carboxy, and amido.

An example of a more preferred amino acid according to the presentinvention is the amino acid lysine having the formula:

wherein R is a substituted C₁ alkyl moiety, said substituent is4-imidazolyl.

Non-limiting examples of preferred amino acids include alanine,arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid,glycine, histidine, isoleucine, leucine, lysine, methionine,phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine,and mixtures thereof. The aforementioned amino acids are typicallyreferred to as the “primary a-amino acids”, however, the proteinaceoussuds stabilizers of the present invention may comprise any amino acidhaving an R unit which together with the aforementioned amino acidsserves to adjust the isoelectric point of the proteinaceous sudsstabilizers to a range of from about 7 to about 11.5. For example,further non-limiting examples of amino acids include homoserine,hydroxyproline, norleucine, norvaline, ornithine, penicillamine, andphenylglycine, preferably ornithine. R units preferably comprisemoieties which are capable of a cationic or anionic charges within therange of pH from about 7 to about 11.5. Non-limiting examples ofpreferred amino acids having anionic R units include glutamic acid,aspartic acid, and g-carboxyglutamic acid.

For the purposes of the present invention, both optical isomers of anyamino acid having a chiral center serve equally well for inclusion intothe backbone of the peptide, polypeptide, or amino acid copolymers.Racemic mixtures of one amino acid may be suitably combined with asingle optical isomer of one or more other amino acids depending uponthe desired properties of the final proteinaceous suds stabilizer. Thesame applies to amino acids capable of forming diasteriomeric pairs, forexample, threonine.

Polyamino Acid Proteinaceous Suds Stabilizer—One type of suitableproteinaceous suds stabilizer according to the present invention iscomprised entirely of the amino acids described herein above. Saidpolyamino acid compounds may be naturally occurring peptides,polypeptides, enzymes, and the like, provided said compounds have anisoelectric point of from about 7 to about 11.5 and a molecular weightgreater than or equal to about 1500 daltons. Preferably theproteinaceous suds stabilizers of the present invention which arecomprised entirely of amino acids, comprise from about 10% to about 40%by weight, of amino acids which are capable of being protonated at a pHof from about 7 to about 11.5. An example of a polyamino acid which issuitable as a proteinaceous suds stabilizer according to the presentinvention is the enzyme lysozyme.

An exception may, from time to time, occur in the case where naturallyoccurring enzymes, proteins, and peptides are chosen as proteinaceoussuds stabilizers. Without wishing to be limited by theory, the uniquesecondary, tertiary, or quaternary structure of said naturally occurringpolypeptides may permit their use even though the amount of protonatableamino acids within the pH range of from about 7 to about 11.5 is outsidethe range of from about 10% to about 40% by weight. For example anenzyme having an isoelectric point in the range of from about 7 to about11.5 which only comprises 5% by weight amino acids having R units whichare protonated at a pH of from about 7 to about 11.5 may suitably serveas an effective proteinaceous suds stabilizer according to the presentinvention.

Another class of suitable polyamino acid compound is the syntheticpeptide having a molecular weight of at least about 1500 daltons andfurther comprising from about 10% to about 40% by weight of amino acidscapable of being protonated at a pH of form about 7 to about 11.5. Inaddition, said polyamino acid peptides must have an isoelectric point ofform 7 to about 11.5, preferably from about 8.5 to about 11.5, morepreferably form about 9.5 to about 11. An example of a polyamino acidsynthetic peptide suitable for use as a proteinaceous suds stabilizeraccording to the present invention is the copolymer of the amino acidslysine, alanine, glutamic acid, and tyrosine having an average molecularweight of 52,000 daltons and a ratio of lys:ala:glu:tyr of approximately5:6:2:1.

Without wishing to be limited by theory, the presence of one or morecationic amino acids, for example, histidine, ornithine, lysine and thelike, is required to insure increased suds stabilization and sudsvolume. However, the relative amount of cationic amino acid present, aswell as the resulting isoelectric point of the polyamino acid, are keyto the effectiveness of the resulting material. For example, polyL-lysine having a molecular weight of approximately 18,000 daltonscomprises 100% amino acids which have the capacity to possess a positivecharge in the pH range of from about 7 to about 11.5, with the resultthat this material is ineffective as a suds extender and as a greasysoil removing agent.

Peptide Copolymers—Another class of materials suitable for use asproteinaceous suds stabilizers according to the present invention arepeptide copolymers. For the purposes of the present invention “peptidecopolymers” are defined as “polymeric materials with a molecular weightgreater than or equal to about 1500 daltons having an isoelectric pointof from about 7 to about 11.5 wherein at least about 10% by weight ofsaid polymeric material comprises one or more amino acids”.

Peptide copolymers suitable for use as proteinaceous suds stabilizersmay include segments of polyethylene oxide which are linked to segmentsof peptide or polypeptide to form a material which has increased sudsretention as well as formulatability.

Nonlimiting examples of amino acid copolymer classes include thefollowing.

A. Polyalkyleneimine Copolymers.

Polyalkyleneimine copolymers comprise random segments ofpolyalkyleneimine, preferably polyethyleneimine, together with segmentsof amino acid residues. For example, tetraethylenepentamine is reactedtogether with polyglutamic acid and polyalanine to form a copolymerhaving the formula:

wherein m is equal to 3, n is equal to 0, i is equal to 3, j is equal to5, x is equal to 3, y is equal to 4, and z is equal to 7.

However, the formulator may substitute other polyamines forpolyalkyleneimines, for example, polyvinyl amines, or other suitablepolyamine which provides for a source of cationic charge at a pH of from7 to abut 11.5 and which results in a copolymer having an isoelectricpoint of from about 7 to about 11.5.

The formulator may combine non-amine polymers with protonatable as wellas non-protonatable amino acids. For example, a carboxylate-containinghomo-polymer may be reacted with one or more amino acids, for example,histidine and glycine, to form an amino acid containing amido copolymerhaving the formula:

wherein said copolymer has a molecular weight of at least 1500 daltonsand a ratio of x:y:z of approximately 2:3:6.

The proteinaceous polymeric suds stabilizers when used in the methods ofthe present invention are present at an effective amount of one or moreproteinaceous suds stabilizers described herein, preferably from about0.3% to about 5%, more preferably from about 0.4% to about 4%, mostpreferably from about 0.5% to about 3% by weight, of said composition.What is meant herein by “an effective amount of proteinaceous sudsstabilizer” is that the suds produced by the presently describedcompositions are sustained for an increased amount of time relative to acomposition which does not comprise a proteinaceous suds stabilizerdescribed herein.

These and other suitable polymeric suds stabilizers and methods forpreparing them, can be found in PCT/US98/24707 filed Nov. 20, 1998.

3 Zwitterionic Polymeric Suds Stabilizers

The zwitterionic polymeric suds stabilizers of the present inventioncomprise monomeric units which have at least one moiety capable ofsustaining a negative charge at a pH of from about 4 to about 12 and atleast one moiety capable of sustaining a positive charge within the samepH range. The zwitterionic polymers may be homopolymers or copolymers,each of which may be suitably crosslinked.

The polymeric suds stabilizers of the present invention are zwitterionicpolymers. For the purposes of the present invention the term“zwitterionic polymer” is defined as “a polymeric material comprised ofone or more monomers wherein each monomer has one or more moietiescapable of sustaining a positive or negative charge at a pH of fromabout 4 to about 12 such that the number of positively charged moietiesis equal to the number of negatively charged moieties at the isoelectricpoint of said polymer.”

The polymeric suds stabilizers of the present invention are homopolymersor copolymers wherein the monomers which comprise said homopolymers orcopolymers contain a moiety capable of being protonated at a pH of fromabout 4 to about 12, or a moiety capable of being de-protonated at a pHof from about 4 to about 12, of a mixture of both types of moieties.

A preferred class of zwitterionic polymer suitable for use as a sudsvolume and suds duration enhancer has the formula:

wherein R is C₁–C₁₂ linear alkylene, C₁–C₁₂ branched alkylene, andmixtures thereof; preferably C₁–C₄ linear alkylene, C₃–C₄ branchedalkylene; more preferably methylene and 1,2-propylene. R¹ and R² aredefined herein after. The index x is from 0 to 6; y is 0 or 1; z is 0 or1.

The index n has the value such that the zwitterionic polymers of thepresent invention have an average molecular weight of from about 1,000to about 2,000,000 preferably from about 5,000 to about 1,000,000, morepreferably from about 10,000 to about 750,000, more preferably fromabout 20,000 to about 500,000, even more preferably from about 35,000 toabout 300,000 daltons. The molecular weight of the polymeric sudsboosters, can be determined via conventional gel permeationchromatography.

Anionic Units—R¹ is a unit capable of having a negative charge at a pHof from about 4 to about 12. Preferred R¹ has the formula:-(L)_(i)-(S)_(j)—R³wherein L is a linking unit independently selected from the following:

andmixtures thereof, wherein R′ is independently hydrogen, C₁–C₄ alkyl, andmixtures thereof; preferably hydrogen or alternatively R′ and S can forma heterocycle of 4 to 7 carbon atoms, optionally containing other heteroatoms and optionally substituted. Preferably the linking group L can beintroduced into the molecule as part of the original monomer backbone,for example, a polymer having L units of the formula:

can suitably have this moiety introduced into the polymer via acarboxylate containing monomer, for example, a monomer having thegeneral formula:

When the index i is 0, L is absent.

For anionic units S is a “spacing unit” wherein each S unit isindependently selected from C₁–C₁₂ linear alkylene, C₁–C₁₂ branchedalkylene, C₃–C₁₂ linear alkenylene, C₃–C₁₂ branched alkenylene, C₃–C₁₂hydroxyalkylene, C₄–C₁₂ dihydroxyalkylene, C₆–C₁₀ arylene, C₈–C₁₂dialkylarylene, —(R⁵O)_(k)R⁵—, —(R⁵O)_(k)R⁶(OR⁵)_(k)—, —CH₂CH(OR⁷)CH₂—,and mixtures thereof; wherein R⁵ is C₂–C₄ linear alkylene, C₃–C₄branched alkylene, and mixtures thereof, preferably ethylene,1,2-propylene, and mixtures thereof, more preferably ethylene; R⁶ isC₂–C₁₂ linear alkylene, and mixtures thereof, preferably ethylene; R⁷ ishydrogen, C₁–C₄ alkyl, and mixtures thereof, preferably hydrogen. Theindex k is from 1 to about 20.

Preferably S is C₁–C₁₂ linear alkylene, —(R⁵O)_(k)R⁵—, and mixturesthereof. When S is a —(R⁵O)_(k)R⁵— unit, said units may be suitablyformed by the addition an alkyleneoxy producing reactant (e.g. ethyleneoxide, epichlorohydrin) or by addition of a suitable polyethyleneglycol.More preferably S is C₂–C₄ linear alkylene. When the index j is 0 the Sunit is absent.

R³ is independently selected from hydrogen, —CO₂M, —SO₃M, —OSO₃M,—CH₂P(O)(OM)₂, —OP(O)(OM)₂, units having the formula:—CR⁸R⁹R¹⁰wherein each R⁸, R⁹, and R¹⁰ is independently selected from the groupconsisting of hydrogen, —(CH₂)_(m)R¹¹, and mixtures thereof, wherein R¹¹is —CO₂H, —SO₃M, —OSO₃M, —CH(CO₂H)CH₂CO₂H, —CH₂P(O)(OH)₂, —OP(O)(OH)₂,and mixtures thereof, preferably —CO₂H, —CH(CO₂H)CH₂CO₂H, and mixturesthereof, more preferably —CO₂H; provided that one R⁸, R⁹, or R¹⁰ is nota hydrogen atom, preferably two R⁸, R⁹, or R¹⁰ units are hydrogen. M ishydrogen or a salt forming cation, preferably hydrogen. The index m hasthe value from 0 to 10.Cationic Units—R² is a unit capable of having a positive charge at a pHof from about 4 to about 12. Preferred R² has the formula:—(L¹)_(i′)—(S)_(j′)—R⁴wherein L¹ is a linking unit independently selected from the following:

and mixtures thereof; wherein R′ is independently hydrogen, C₁–C₄ alkyl,and mixtures thereof; preferably hydrogen or alternatively R′ and S canform a heterocycle of 4 to 7 carbon atoms, optionally containing otherhetero atoms and optionally substituted.Preferably L¹ has the Formula:

When the index i′ is equal to 0, L¹ is absent.

For cationic units S is a “spacing unit” wherein each S unit isindependently selected from C₁–C₁₂ linear alkylene, C₁–C₁₂ branchedalkylene, C₃–C₁₂ linear alkenylene, C₃–C₁₂ branched alkenylene, C₃–C₁₂hydroxyalkylene, C₄–C₁₂ dihydroxyalkylene, C₆–C₁₀ arylene, C₈–C₁₂dialkylarylene, —(R⁵O)_(k)R⁵—, —(R⁵O)_(k)R⁶(OR⁵)_(k)—, —CH₂CH(OR⁷)CH₂—,and mixtures thereof; wherein R⁵ is C₂–C₄linear alkylene, C₃–C₄ branchedalkylene, and mixtures thereof, preferably ethylene, 1,2-propylene, andmixtures thereof, more preferably ethylene; R⁶ is C₂–C₁₂ linearalkylene, and mixtures thereof, preferably ethylene; R⁷ is hydrogen,C₁–C₄ alkyl, and mixtures thereof, preferably hydrogen. The index k isfrom 1 to about 20.

Preferably S is C₁–C₁₂ linear alkylene, and mixtures thereof. PreferablyS is C₂–C₄ linear alkylene. When the index j′ is 0 the S unit is absent.

R⁴ is independently selected from amino, alkylamino carboxamide,3-imidazolyl, 4-imidazolyl, 2-imidazolinyl, 4-imidazolinyl,2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1-pyrazolyl, 3-pyrazoyl,4-pyrazoyl, 5-pyrazoyl, 1-pyrazolinyl, 3-pyrazolinyl, 4-pyrazolinyl,5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, piperazinyl,2-pyrrolidinyl, 3-pyrrolidinyl, guanidino, amidino, and mixturesthereof, preferably dialkylamino having the formula:—N(R¹¹)₂wherein each R¹¹ is independently hydrogen, C₁–C₄ alkyl, and mixturesthereof, preferably hydrogen or methyl or alternatively the two R¹¹ canform a heterocycle of 4 to 8 carbon atoms, optionally containing otherhetero atoms and optionally substituted.

An example of a preferred zwitterionic polymer according to the presentinvention has the formula:

wherein X is C₆, n has a value such that the average molecular weight isfrom about 5,000 to about 1,000,000 daltons.

Further preferred zwitterionic polymers according to the presentinvention are polymers comprising monomers wherein each monomer has onlycationic units or anionic units, said polymers have the formula:

wherein R, R¹, x, y, and z are the same as defined herein above; n¹+n²=nsuch that n has a value wherein the resulting zwitterionic polymer has amolecular weight of form about 5,000 to about 1,000,000 daltons.

An example of a polymer having monomers with only an anionic unit or acationic unit has the formula:

wherein the sum of n¹ and n² provide a polymer with an average molecularweight of from about 5,000 to about 750,000 daltons.

Another preferred zwitterionic polymer according to the presentinvention are polymers which have limited crosslinking, said polymershaving the formula:

wherein R, R¹, L¹, S, j′, x, y, and z are the same as defined hereinabove; n′ is equal to n″, and the value n′+n″ is less than or equal to5% of the value of n ¹+n²=n; n provides a polymer with an averagemolecular weight of from about 1,000 to about 2,000,000 daltons. R¹² isnitrogen, C₁–C₁₂ linear alkylene amino alkylene having the formula:—R¹³—N—R¹³—L¹, and mixtures thereof, wherein each R¹³ is independently L¹ orethylene.

The zwitterionic polymers of the present invention may comprise anycombination of monomer units, for example, several different monomershaving various R¹ and R² groups can be combined to form a suitable sudsstabilizer. Alternatively the same R¹ unit may be used with a selectionof different R² units and vice versa.

The zwitterionic polymeric suds stabilizers when used in the methods ofthe present invention are present at an effective amount, preferablyfrom about 0.01% to about 10%, more preferably from about 0.05% to about5%, most preferably from about 0.1% to about 2% by weight, of saidcomposition. What is meant herein by “an effective amount ofzwitterionic polymeric suds stabilizer” is that the suds produced by thepresently described compositions are sustained for an increased amountof time relative to a composition which does not comprise a zwitterionicpolymeric suds stabilizer described herein. Additionally, the polymericsuds stabilizer can be present as the free base or as a salt. Typicalcounter ions include, citrate, maleate, sulfate, chloride, etc.

These and other suitable polymeric suds stabilizers and methods ofpreparing them, can be found in PCT/US98/24699 filed Nov. 20, 1998(Docket No. 6943).

4. Polymers Comprising Units Capable of Having a Cationic Charge

The fourth aspect of the present invention relates to polymericmaterials which provide enhanced suds duration and enhanced suds volumewhen formulated into detergent compositions. The polymeric material maycomprise any material provided the final polymers have an averagecationic charge density of from about 0.0005 to about 0.05 units per 100daltons molecular weight at a pH of from about 4 to about 12. Preferablythe average cationic charge density is from about 0.005 to about 0.03unit per 100 daltons molecular weight.

It is preferred that the polymeric suds stabilizer further comprises:

-   -   ii) units capable of having an anionic charge at a pH of from        about 4 to about 12;    -   iii) units capable of having an anionic charge and a cationic        charge at a pH of from about 4 to about 12;    -   iv) units having no charge at a pH of from about 4 to about 12;        and    -   v) mixtures of units (i), (ii), (iii), and (iv);

The polymeric suds stabilizers of the present invention can be polymerswhich contain units capable of having a cationic charge at a pH of fromabout 4 to about 12, provided that the suds stabilizer has an averagecationic charge density from about 0.0005 to about 0.05 units per 100daltons molecular weight at a pH of from about 4 to about 12.Additionally, the polymeric suds stabilizer can be present as the freebase or as a salt. Typical counter ions include, citrate, maleate,sulfate, chloride, etc.

For the purposes of the present invention the term “cationic unit” isdefined as “a moiety which when incorporated into the structure of thesuds stabilizers of the present invention, is capable of maintaining acationic charge within the pH range of from about 4 to about 12. Thecationic unit is not required to be protonated at every pH value withinthe range of about 4 to about 12.” Non-limiting examples of units whichcomprise a cationic moiety include lysine, ornithine, the monomeric unithaving the formula:

the monomeric unit having the formula:

the monomeric unit having the formula:

the monomeric unit having the formula:

and the monomeric unit having the formula:

the latter of which also comprises a moiety capable of having an anioniccharge at a pH of about 4 to about 12.

For the purposes of the present invention the term “anionic unit” isdefined as “a moiety which when incorporated into the structure of thesuds stabilizers of the present invention, is capable of maintaining ananionic charge within the pH range of from about 4 to about 12. Theanionic unit is not required to be de-protonated at every pH valuewithin the range of about 4 to about 12.” Non-limiting examples of unitswhich comprise a anionic moiety include, acrylic acid, methacrylic acid,glutamic acid, aspartic acid, the monomeric unit having the formula:

and the monomeric unit having the formula:

the latter of which also comprises a moiety capable of having a cationiccharge at a pH of about 4 to about 12. This latter unit is definedherein as “a unit capable of having an anionic and a cationic charge ata pH of from about 4 to about 12.”

For the purposes of the present invention the term “non-charged unit” isdefined as “a moiety which when incorporated into the structure of thesuds stabilizers of the present invention, has no charge within the pHrange of from about 4 to about 12.” Non-limiting examples of units whichare “non-charged units” are styrene, ethylene, propylene, butylene,1,2-phenylene, esters, amides, ketones, ethers, and the like.

The units which comprise the polymers of the present invention may, assingle units or monomers, have any pK_(a) value.

The following are non-limiting examples of suitable polymeric materialsaccording to the present invention. The following examples are presentedin “classes”, however, the formulator may combine any suitable monomersor units to form a polymeric suds stabilizer, for example, amino acidsmay be combined with polyacrylate units.

The polymeric suds stabilizers polymers which contain units capable ofhaving a cationic charge also include polymers comprising at least onemonomeric unit of the formula:

wherein each of R¹, R², R³, R⁴, L, Z, z, and A are hereinbefore defined.Furthermore, suitable polymers include copolymers of

wherein R¹ L and B are as hereinbefore defined, and copolymers of

wherein R¹, R¹², R¹³, Z and z are as hereinbefore defined,

The suds stabilizers polymers which contain units capable of having acationic charge may proteinaceous suds stabilizers, as herein beforedescribed, including peptides, polypeptides, amino acid containingcopolymers, terpolymers etc., and mixtures thereof. Any suitable aminoacid can be used to form the backbone of the peptides, polypeptides, oramino acid, wherein the polymers have an average cationic charge densityfrom about 0.0005 to about 0.05 units per 100 daltons molecular weightat a pH of from about 4 to about 12.

In general, the amino acids suitable for use in forming theproteinaceous suds stabilizers of the present invention have theformula:

wherein R, R¹, R², x and y and are as hereinbefore defined.

The polymeric suds stabilizers polymers which contain units capable ofhaving a cationic charge may be homopolymers or copolymers wherein themonomers which comprise said homopolymers or copolymers contain a moietycapable of being protonated at a pH of from about 4 to about 12, or amoiety capable of being de-protonated at a pH of from about 4 to about12, of a mixture of both types of moieties. These suitable zwitterionicpolymers are hereinbefore defined.

A Preferred class of suitable for use as a suds volume and suds durationenhancer has the formula:

wherein R, R¹, R², x, y, z, and n are hereinbefore defined. Furthermoresuitable anionic, cationic and, zwitterionic monomers are also hereinbefore described.Cationic Charge Density—For the purposes of the methods of the presentinvention the term “cationic charge density” is defined as “the numberof units that are protonated at a specific pH per 100 daltons mass ofpolymer.”

For illustrative purposes only, a polypeptide comprising 10 units of theamino acid lysine has a molecular weight of approximately 1028 daltons,wherein there are 11 —NH₂ units. If at a specific pH within the range offrom about 4 to about 12, 2 of the —NH₂ units are protonated in the formof —NH₃ ⁺, then the cationic charge density is 2 cationic chargeunits÷by 1028 daltons molecular weight=approximately 0.002 units ofcationic charge per 100 daltons. This would, therefore, have sufficientcationic charge to suffice the cationic charge density of the presentinvention, but insufficient molecular weight to be a suitable sudsenhancer.

Polymers have been shown to be effective for delivering sudsing benefitsprovided the polymer contains a cationic moiety, either permanent via aquaternary nitrogen or temporary via protonation. Without being limitedby theory, it is believed that the cationic charge must be sufficient toattract the polymer to negatively charged soils but not so large as tocause negative interactions with available anionic surfactants.Herewithin the term cationic charge density is defined as the amount ofcationic charge on a given polymer, either by permanent cationic groupsor via protonated groups, as a weight percent of the total polymer atthe desired wash pH. For example, with poly(-DMAM), we haveexperimentally determined the pKa, see hereinafter as to how pKa ismeasured, of this polymer to be 7.0. Thus, if the wash pH is 7.0, thenhalf of the available nitrogens will be protonated (and count ascationic) and the other half will not be protonated (and not be countedin the “cationic charge density”). Thus, since the Nitrogen has amolecular weight of approximately 14 grams/mole, and the DMAM monomerhas a molecular weight of approximately 157 grams/mole, the can becalculated:Cationic Charge Density=(14/157)*50%=0.0446 or 4.46%.Thus, 4.46% of the polymer contains cationic charges. As anotherexample, one could make a copolymer of DMAM with DMA, where the ratio ofmonomers is 1 mole of DMAM for 3 moles of DMA. The DMA monomer has amolecular weight of 99 grams/mole. In this case the pKa has beenmeasured to be 7.6. Thus, if the wash pH is 5.0, all of the availablenitrogens will be protonated. The cationic charge density is thencalculated:Cationic Charge Density=14/(157+99+99+99)*100%=0.0103, or 1.03%.Notice that in this example, the minimum repeating unit is considered 1DMAM monomer plus 3 DMA monomers.

A key aspect of this calculation is the pKa measurement for anyprotonatable species which will result in a cationic charge on theheteroatom. Since the pKa is dependent on the polymer structure andvarious monomers present, this must be measure to determine thepercentage of protonatable sites to count as a function of the desiredwash pH. This is an easy exercise for one skilled in the art.

Based on this calculation, the percent of cationic charge is independentof polymer molecular weight.

The pKa of a polymeric suds booster is determined in the followingmanner. Make at least 50 mls of a 5% polymer solution, such as a polymerprepared according to any of Examples 1 to 5 as described hereinafter,in ultra pure water (i.e. no added salt). At 25° C., take initial pH ofthe 5% polymer solution with a pH meter and record when a steady readingis achieved. Maintain temperature throughout the test at 25° C. with awater bath and stir continuously. Raise pH of 50 mls of the aqueouspolymer solution to 12 using NaOH (1N, 12.5M). Titrate 5 mls of 0.1N HClinto the polymer solution. Record pH when steady reading is achieved.Repeat steps 4 and 5 until pH is below 3. The pKa was determined from aplot of pH vs. volume of titrant using the standard procedure asdisclosed in Quantitative Chemical Analysis, Daniel C. Harris, W.H.Freeman & Chapman, San Francisco, USA 1982.

The detergent compositions for use in the methods of the presentinvention comprising polymers which contain units capable of having acationic charge comprise at least an effective amount of one or morepolymeric suds stabilizers described herein, preferably from about 0.01%to about 10%, more preferably from about 0.05% to about 5%, mostpreferably from about 0.1% to about 2% by weight, of said composition.What is meant herein by “an effective amount of polymeric sudsstabilizer” is that the suds produced by the presently describedcompositions are sustained for an increased amount of time relative to acomposition which does not comprise a polymeric suds stabilizerdescribed herein.

These and other suitable polymeric suds stabilizers and methods ofpreparing them, can be found in PCT/US98/24852 filed Nov. 20, 1998(Docket No. 6944).

Detersive Surfactants

The compositions of the present invention preferably contain a detersivesurfactant. The detersive surfacatnt is typically selected from thegroup consisting of anionic, nonionics, cationics, ampholytics,zwitterionics, and mixtures thereof. By selecting the type and amount ofdetersive surfactant, along with other adjunct ingredients disclosedherein, the present detergent compositions can be formulated to be usedin the context of laundry cleaning or in other different cleaningapplications, particularly including dishwashing. The particularsurfactants used can therefore vary widely depending upon the particularend-use envisioned. Suitable surfactants are described below. Examplesof suitable nonionic, anionic, cationic amphoteric and zwitterionicsurfactants are given in “Surface Active Agents and Detergents” (Vol. Iand II by Schwartz, Perry and Berch). A variety of such surfactants arealso generally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30,1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line23.

Anionic Surfactants—Anionic surfactants useful in the present inventionare preferably selected from the group consisting of, linearalkylbenzene sulfonate, alpha olefin sulfonate, paraffin sulfonates,alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfate, alkylsulfonates, alkyl alkoxy carboxylate, alkyl alkoxylated sulfates,sarcosinates, taurinates, and mixtures thereof. An effective amount,typically from about 0.5% to about 90%, preferably about 5% to about60%, more preferably from about 10 to about 30%, by weight of anionicdetersive surfactant can be used in the present invention.

Alkyl sulfate surfactants are another type of anionic surfactant ofimportance for use herein. In addition to providing excellent overallcleaning ability when used in combination with polyhydroxy fatty acidamides (see below), including good grease/oil cleaning over a wide rangeof temperatures, wash concentrations, and wash times, dissolution ofalkyl sulfates can be obtained, as well as improved formulability inliquid detergent formulations are water soluble salts or acids of theformula ROSO₃M wherein R preferably is a C₁₀–C₂₄ hydrocarbyl, preferablyan alkyl or hydroxyalkyl having a C₁₀–C₂₀ alkyl component, morepreferably a C₁₂–C₁₈ alkyl or hydroxyalkyl, and M is H or a cation,e.g., an alkali (Group IA) metal cation (e.g., sodium, potassium,lithium), substituted or unsubstituted ammonium cations such as methyl-,dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g.,tetramethyl-ammonium and dimethyl piperdinium, and cations derived fromalkanolamines such as ethanolamine, diethanolamine, triethanolamine, andmixtures thereof, and the like. Typically, alkyl chains of C₁₂₋₁₆ arepreferred for lower wash temperatures (e.g., below about 50° C.) andC₁₆₋₁₈ alkyl chains are preferred for higher wash temperatures (e.g.,above about 50° C.).

Alkyl alkoxylated sulfate surfactants are another category of usefulanionic surfactant. These surfactants are water soluble salts or acidstypically of the formula RO(A)_(m)SO₃M wherein R is an unsubstitutedC₁₀–C₂₄ alkyl or hydroxyalkyl group having a C₁₀–C₂₄ alkyl component,preferably a C₁₂–C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂–C₁₈alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater thanzero, typically between about 0.5 and about 6, more preferably betweenabout 0.5 and about 3, and M is H or a cation which can be, for example,a metal cation (e.g., sodium, potassium, lithium, etc.), ammonium orsubstituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkylpropoxylated sulfates are contemplated herein. Specific examples ofsubstituted ammonium cations include methyl-, dimethyl-,trimethyl-ammonium and quaternary ammonium cations, such astetramethyl-ammonium, dimethyl piperidinium and cations derived fromalkanolamines, e.g. monoethanolamine, diethanolamine, andtriethanolamine, and mixtures thereof. Exemplary surfactants are C₁₂–C₁₈alkyl polyethoxylate (1.0) sulfate, C₁₂–C₁₈ alkyl polyethoxylate (2.25)sulfate, C₁₂–C₁₈ alkyl polyethoxylate (3.0) sulfate, and C₁₂–C₁₈ alkylpolyethoxylate (4.0) sulfate wherein M is conveniently selected fromsodium and potassium. Surfactants for use herein can be made fromnatural or synthetic alcohol feedstocks. Chain lengths represent averagehydrocarbon distributions, including branching.

Additionally and preferably, the surfactant may be a midchain branchedalkyl sulfate, midchain branched alkyl alkoxylate, or midchain branchedalkyl alkoxylate sulfate. These surfactants are further described in No.60/061,971, Oct. 14, 1997, No. 60/061,975, Oct. 14, 1997, No.60/062,086, Oct. 14, 1997, No. 60/061,916, Oct. 14, 1997, No.60/061,970, Oct. 14, 1997, No. 60/062,407, Oct. 14, 1997. Other suitablemid-chain branched surfactants can be found in U.S. Patent applicationSer. Nos. 60/032,035, 60/031,845, 60/031,916, 60/031,917, 60/031,761,60/031,762 and 60/031,844. Mixtures of these branched surfactants withconventional linear surfactants are also suitable for use in the presentcompositions.

Another prefered anionic surfactant are the so-called modified alkylbenzene sulfonate surfactants, or MLAS. Some suitable MLAS surfactants,methods of making them and exempliary compositions are further describedin copending U.S. Patent application Ser. Nos. 60/053,319, 60/053,318,60/053,321, 60/053,209, 60/053,328, 60/053,186, 60/055,437, 60/105,017,and 60/104,962.

Examples of suitable anionic surfactants are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).

Nonionic Detergent Surfactants—Suitable nonionic detergent surfactantsare generally disclosed in U.S. Pat. No. 3,929,678, Laughlin et al.,issued Dec. 30, 1975, at column 13, line 14 through column 16, line 6,incorporated herein by reference. Exemplary, non-limiting classes ofuseful nonionic surfactants include: amine oxides, alkyl ethoxylate,alkanoyl glucose amide, alkyl betaines, sulfobetaine and mixturesthereof.

Amine oxides are semi-polar nonionic surfactants and includewater-soluble amine oxides containing one alkyl moiety of from about 10to about 18 carbon atoms and 2 moieties selected from the groupconsisting of alkyl groups and hydroxyalkyl groups containing from about1 to about 3 carbon atoms; water-soluble phosphine oxides containing onealkyl moiety of from about 10 to about 18 carbon atoms and 2 moietiesselected from the group consisting of alkyl groups and hydroxyalkylgroups containing from about 1 to about 3 carbon atoms; andwater-soluble sulfoxides containing one alkyl moiety of from about 10 toabout 18 carbon atoms and a moiety selected from the group consisting ofalkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxidesurfactants having the formula

wherein R³ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixturesthereof containing from about 8 to about 22 carbon atoms; R⁴ is analkylene or hydroxyalkylene group containing from about 2 to about 3carbon atoms or mixtures thereof; x is from 0 to about 3; and each R⁵ isan alkyl or hydroxyalkyl group containing from about 1 to about 3 carbonatoms or a polyethylene oxide group containing from about 1 to about 3ethylene oxide groups. The R⁵ groups can be attached to each other,e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C₁₀–C₁₈ alkyldimethyl amine oxides and C₈–C₁₂ alkoxy ethyl dihydroxy ethyl amineoxides. Preferably the amine oxide is present in the composition in aneffective amount, more preferably from about 0.1% to about 20%, evenmore preferably about 0.1% to about 15%, even more preferably still fromabout 0.5% to about 10%, by weight.

The polyethylene, polypropylene, and polybutylene oxide condensates ofalkyl phenols. In general, the polyethylene oxide condensates arepreferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to about 12 carbonatoms in either a straight chain or branched chain configuration withthe alkylene oxide. In a preferred embodiment, the ethylene oxide ispresent in an amount equal to from about 5 to about 25 moles of ethyleneoxide per mole of alkyl phenol. Commercially available nonionicsurfactants of this type include Igepal® CO-630, marketed by the GAFCorporation; and Triton® X-45, X-114, X-100, and X-102, all marketed bythe Rohm & Haas Company. These compounds are commonly referred to asalkyl phenol alkoxylates, (e.g., alkyl phenol ethoxylates).

The condensation products of aliphatic alcohols with from about 1 toabout 25 moles of ethylene oxide. The alkyl chain of the aliphaticalcohol can either be straight or branched, primary or secondary, andgenerally contains from about 8 to about 22 carbon atoms. Particularlypreferred are the condensation products of alcohols having an alkylgroup containing from about 10 to about 20 carbon atoms with from about2 to about 18 moles of ethylene oxide per mole of alcohol. Examples ofcommercially available nonionic surfactants of this type includeTergitol® 15-S-9 (the condensation product of C₁₁–C₁₅ linear secondaryalcohol with 9 moles ethylene oxide), Tergitol® 24-L-6 NMW (thecondensation product of C₁₂–C₁₄ primary alcohol with 6 moles ethyleneoxide with a narrow molecular weight distribution), both marketed byUnion Carbide Corporation; Neodol® 45-9 (the condensation product ofC₁₄–C₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol® 23-6.5(the condensation product of C₁₂–C₁₃ linear alcohol with 6.5 moles ofethylene oxide), Neodol® 45-7 (the condensation product of C₁₄–C₁₅linear alcohol with 7 moles of ethylene oxide), Neodol® 45-4 (thecondensation product of C₁₄–C₁₅ linear alcohol with 4 moles of ethyleneoxide), marketed by Shell Chemical Company, and Kyro® EOB (thecondensation product of C₁₃–C₁₅ alcohol with 9 moles ethylene oxide),marketed by The Procter & Gamble Company. Other commercially availablenonionic surfactants include Dobanol 91-8® marketed by Shell ChemicalCo. and Genapol UD-080® marketed by Hoechst. This category of nonionicsurfactant is referred to generally as “alkyl ethoxylates.”

The preferred alkylpolyglycosides have the formulaR²O(C_(n)H_(2n)O)_(t)(glycosyl)_(x)wherein R² is selected from the group consisting of alkyl, alkyl-phenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably 0; and x is from about 1.3 to about 10, preferablyfrom about 1.3 to about 3, most preferably from about 1.3 to about 2.7.The glycosyl is preferably derived from glucose. To prepare thesecompounds, the alcohol or alkylpolyethoxy alcohol is formed first andthen reacted with glucose, or a source of glucose, to form the glucoside(attachment at the 1-position). The additional glycosyl units can thenbe attached between their 1-position and the preceding glycosyl units2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.

Fatty acid amide surfactants having the formula:

wherein R⁶ is an alkyl group containing from about 7 to about 21(preferably from about 9 to about 17) carbon atoms and each R⁷ isselected from the group consisting of hydrogen, C₁–C₄ alkyl, C₁–C₄hydroxyalkyl, and —(C²H₄O)_(x)H where x varies from about 1 to about 3.

Preferred amides are C₈–C₂₀ ammonia amides, monoethanolamides,diethanolamides, and isopropanolamides.

Preferably the nonionic surfactant, when present in the composition, ispresent in an effective amount, more preferably from about 0.1% to about20%, even more preferably about 0.1% to about 15%, even more preferablystill from about 0.5% to about 10%, by weight.

Polyhydroxy Fatty Acid Amide Surfactant—The detergent compositionshereof may also contain an effective amount of polyhydroxy fatty acidamide surfactant. By “effective amount” is meant that the formulator ofthe composition can select an amount of polyhydroxy fatty acid amide tobe incorporated into the compositions that will improve the cleaningperformance of the detergent composition. In general, for conventionallevels, the incorporation of about 1%, by weight, polyhydroxy fatty acidamide will enhance cleaning performance.

The detergent compositions herein will typically comprise about 1%weight basis, polyhydroxy fatty acid amide surfactant, preferably fromabout 3% to about 30%, of the polyhydroxy fatty acid amide. Thepolyhydroxy fatty acid amide surfactant component comprises compounds ofthe structural formula:

wherein: R¹ is H, C₁–C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl,or a mixture thereof, preferably C₁–C₄ alkyl, more preferably C₁ or C₂alkyl, most preferably C1 alkyl (i.e., methyl); and R² is a C₅–C₃₁hydrocarbyl, preferably straight chain C₇–C₁₉ alkyl or alkenyl, morepreferably straight chain C₉–C₁₇ alkyl or alkenyl, most preferablystraight chain C₁₁–C₁₅ alkyl or alkenyl, or mixtures thereof; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z preferably will bederived from a reducing sugar in a reductive amination reaction; morepreferably Z will be a glycityl. Suitable reducing sugars includeglucose, fructose, maltose, lactose, galactose, mannose, and xylose. Asraw materials, high dextrose corn syrup, high fructose corn syrup, andhigh maltose corn syrup can be utilized as well as the individual sugarslisted above. These corn syrups may yield a mix of sugar components forZ. It should be understood that it is by no means intended to excludeother suitable raw materials. Z preferably will be selected from thegroup consisting of —CH₂—(CHOH)_(n)—CH₂OH,—CH(CH₂OH)—(CHOH)_(n-1)—CH₂OH, —CH₂—(CHOH)₂(CHOR′)(CHOH)—CH₂OH, andalkoxylated derivatives thereof, where n is an integer from 3 to 5,inclusive, and R′ is H or a cyclic or aliphatic monosaccharide. Mostpreferred are glycityls wherein n is 4, particularly —CH₂—(CHOH)₄—CH₂OH.

R′ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl,N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.

R²—CO—N<can be, for example, cocamide, stearamide, oleamide, lauramide,myristamide, capricamide, palmitamide, tallowamide, etc.

Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl,1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl,1-deoxymaltotriotityl, etc.

Methods for making polyhydroxy fatty acid amides are known in the art.In general, they can be made by reacting an alkyl amine with a reducingsugar in a reductive amination reaction to form a corresponding N-alkylpolyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with afatty aliphatic ester or triglyceride in a condensation/amidation stepto form the N-alkyl, N-polyhydroxy fatty acid amide product. Processesfor making compositions containing polyhydroxy fatty acid amides aredisclosed, for example, in G.B. Patent Specification 809,060, publishedFeb. 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Pat. No. 2,965,576,issued Dec. 20, 1960 to E. R. Wilson, and U.S. Pat. No. 2,703,798,Anthony M. Schwartz, issued Mar. 8, 1955, and U.S. Pat. No. 1,985,424,issued Dec. 25, 1934 to Piggott, each of which is incorporated herein byreference.

Diamines—The preferred liquid detergent compositions, such as light dutyliquid, LDL compositions, useful in the methods of the present inventionmay further comprise one or more diamines, preferably an amount ofdiamine such that the ratio of anionic surfactant present to the diamineis from about 40:1 to about 2:1. Said diamines provide for increasedremoval of grease and greasy food material while maintaining suitablelevels of suds.

The diamines suitable for use in the compositions of the presentinvention have the formula:

-   -   wherein each R²⁰ is independently selected from the group        consisting of hydrogen, C₁–C₄ linear or branched alkyl,        alkyleneoxy having the formula:        —(R²¹O)_(y)R²²        wherein R²¹ is C₂–C₄ linear or branched alkylene, and mixtures        thereof; R²² is hydrogen, C₁–C₄ alkyl, and mixtures thereof; y        is from 1 to about 10; X is a unit selected from:

-   i) C₃–C₁₀ linear alkylene, C₃–C₁₀ branched alkylene, C₃–C₁₀ cyclic    alkylene, C₃–C₁₀ branched cyclic alkylene, an alkyleneoxyalkylene    having the formula:    —(R²¹O)_(y)R²¹—

wherein R²¹ and y are the same as defined herein above;

-   ii) C₃–C₁₀ linear, C₃–C₁₀ branched linear, C₃–C₁₀ cyclic, C₃–C₁₀    branched cyclic alkylene, C₆–C₁₀ arylene, wherein said unit    comprises one or more electron donating or electron withdrawing    moieties which provide said diamine with a pK_(a) greater than about    8; and-   iii) mixtures of (i) and (ii)    provided said diamine has a pK_(a) of at least about 8.

The preferred diamines of the present invention have a pK₁ and pK₂ whichare each in the range of from about 8 to about 11.5, preferably in therange of from about 8.4 to about 11, more preferably from about 8.6 toabout 10.75. For the purposes of the present invention the term “pK_(a)”stands equally well for the terms “pK₁” and “pK₂” either separately orcollectively. The term pK_(a) as used herein throughout the presentspecification in the same manner as used by those of ordinary skill inthe art. pK_(a) values are readily obtained from standard literaturesources, for example, “Critical Stability Constants: Volume 2, Amines”by Smith and Martel, Plenum Press, N.Y. and London, (1975).

As an applied definition herein, the pK_(a) values of the diamines arespecified as being measured in an aqueous solution at 25° C. having anionic strength of from about 0.1 to about 0.5 M. As used herein, thepK_(a) is an equilibrium constant dependent upon temperature and ionicstrength, therefore, value reported by literature references, notmeasured in the above described manner, may not be within full agreementwith the values and ranges which comprise the present invention. Toeliminate ambiguity, the relevant conditions and/or references used forpK_(a)'s of this invention are as defined herein or in “CriticalStability Constants: Volume 2, Amines”. One typical method ofmeasurement is the potentiometric titration of the acid with sodiumhydroxide and determination of the pK_(a) by suitable methods asdescribed and referenced in “The Chemist's Ready Reference Handbook” byShugar and Dean, McGraw Hill, NY, 1990.

Preferred diamines for performance and supply considerations are1,3-bis(methylamino)cyclohexane, 1,3-diaminopropane (pK₁=10.5; pK₂=8.8),1,6-diaminohexane (pK₁=11; pK₂=10), 1,3-diaminopentane (Dytek EP)(pK₁=10.5; pK₂=8.9), 2-methyl 1,5-diaminopentane (Dytek A) (pK₁=11.2;pK₂=10.0). Other preferred materials are the primary/primary diamineshaving alkylene spacers ranging from C₄–C₈. In general, primary diaminesare preferred over secondary and tertiary diamines.

The following are non-limiting examples of diamines suitable for use inthe present invention.

1-N,N-dimethylamino-3-aminopropane having the formula:

1,6-diaminohexane having the formula:

1,3-diaminopropane having the formula:

2-methyl-1,5-diaminopentane having the formula:

1,3-diaminopentane, available under the tradename Dytek EP, having theformula:

1,3-diaminobutane having the formula:

Jeffamine EDR 148, a diamine having an alkyleneoxy backbone, having theformula:

3-methyl-3-aminoethyl-5-dimethyl-1-aminocyclohexane (isophorone diamine)having the formula:

1,3-bis(methylamino)cyclohexane having the formula:

Adjunct Ingredients

The compositions used in the methods of the present invention mayfurther comprise an adjunct ingredient. These will be selected dependingupon the desired form and/or application, LDL, personal cleansingcomposition, etc., of the composition. More than one adjunct ingredientcan be incorporated in to the compositions used in the methods.

One highly prefered composition suitable for use in the methods of thepresent invention includes in addition to the polymeric suds stabilizer,an anionic surfactant, more preferably an alky ethoxy sulfonate, evenmore preferably an alky ethoxy sulfonate which contains about 0.6ethoxylates, an amine oxide surfactant, and an enzyme selected from thegroup consisting of amylase, protease, and mixtures thereof.

Builder—The compositions used in the methods of the according to thepresent invention may further comprise a builder system. Anyconventional builder system is suitable for use herein includingaluminosilicate materials, silicates, polycarboxylates and fatty acids,materials such as ethylene-diamine tetraacetate, metal ion sequestrantssuch as aminopolyphosphonates, particularly ethylenediaminetetramethylene phosphonic acid and diethylene triaminepentamethylene-phosphonic acid. Though less preferred for obviousenvironmental reasons, phosphate builders can also be used herein.

Suitable polycarboxylates builders for use herein include citric acid,preferably in the form of a water-soluble salt, derivatives of succinicacid of the formula R—CH(COOH)CH₂(COOH) wherein R is C10⁻²⁰ alkyl oralkenyl, preferably C12–16, or wherein R can be substituted withhydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examplesinclude lauryl succinate, myristyl succinate, palmityl succinate2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders arepreferably used in the form of their water-soluble salts, includingsodium, potassium, ammonium and alkanolammonium salts.

Other suitable polycarboxylates are oxodisuccinates and mixtures oftartrate monosuccinic and tartrate disuccinic acid such as described inU.S. Pat. No. 4,663,071.

Especially for the liquid execution herein, suitable fatty acid buildersfor use herein are saturated or unsaturated C10–18 fatty acids, as wellas the corresponding soaps. Preferred saturated species have from 12 to16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acidis oleic acid. Other preferred builder system for liquid compositions isbased on dodecenyl succinic acid and citric acid.

Detergency builder salts are normally included in amounts of from 3% to50% by weight of the composition preferably from 5% to 30% and mostusually from 5% to 25% by weight.

Enzymes—Detergent compositions used in the methods of the presentinvention may further comprise one or more enzymes which providecleaning performance benefits. Said enzymes include enzymes selectedfrom cellulases, hemicellulases, peroxidases, proteases, gluco-amylases,amylases, lipases, cutinases, pectinases, xylanases, reductases,oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases,tannases, pentosanases, malanases, β-glucanases, arabinosidases ormixtures thereof. A preferred combination is a detergent compositionhaving a cocktail of conventional applicable enzymes like protease,amylase, lipase, cutinase and/or cellulase. Enzymes when present in thecompositions, at from about 0.0001% to about 5% of active enzyme byweight of the detergent composition.

Proteolytic Enzyme—The proteolytic enzyme can be of animal, vegetable ormicroorganism (preferred) origin. The proteases for use in the detergentcompositions herein include (but are not limited to) trypsin,subtilisin, chymotrypsin and elastase-type proteases. Preferred for useherein are subtilisin-type proteolytic enzymes. Particularly preferredis bacterial serine proteolytic enzyme obtained from Bacillus subtilisand/or Bacillus licheniformis.

Suitable proteolytic enzymes include Novo Industri A/S Alcalase®(preferred), Esperase®, Savinase® (Copenhagen, Denmark), Gist-brocades'Maxatase®, Maxacal® and Maxapem 15® (protein engineered Maxacal®)(Delft, Netherlands), and subtilisin BPN and BPN′ (preferred), which arecommercially available. Preferred proteolytic enzymes are also modifiedbacterial serine proteases, such as those made by GenencorInternational, Inc. (San Francisco, Calif.) which are described inEuropean Patent 251,446B, granted Dec. 28, 1994 (particularly pages 17,24 and 98) and which are also called herein “Protease B”. U.S. Pat. No.5,030,378, Venegas, issued Jul. 9, 1991, refers to a modified bacterialserine proteolytic enzyme (Genencor International) which is called“Protease A” herein (same as BPN′). In particular see columns 2 and 3 ofU.S. Pat. No. 5,030,378 for a complete description, including aminosequence, of Protease A and its variants. Other proteases are sold underthe tradenames: Primase, Durazym, Opticlean and Optimase. Preferredproteolytic enzymes, then, are selected from the group consisting ofAlcalase® (Novo Industri A/S), BPN′, Protease A and Protease B(Genencor), and mixtures thereof. Protease B is most preferred.

Of particular interest for use herein are the proteases described inU.S. Pat. No. 5,470,733.

Also proteases described in our co-pending application U.S. Ser. No.08/136,797 can be included in the detergent composition of theinvention.

Another preferred protease, referred to as “Protease D”, is a carbonylhydrolase variant described in WO 95/10615 published Apr. 20, 1995 byGenencor International (A. Baeck et al. entitled “Protease-ContainingCleaning Compositions” having U.S. Ser. No. 08/322,676, filed Oct. 13,1994).

Useful proteases are also described in PCT publications: WO 95/30010published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/30011published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/29979published Nov. 9, 1995 by The Procter & Gamble Company.

Protease enzyme may be incorporated into the compositions in accordancewith the invention at a level of from 0.0001% to 2% active enzyme byweight of the composition.

Amylase—Amylases (α and/or β) can be included for removal ofcarbohydrate-based stains. Suitable amylases are Termamyl® (NovoNordisk), Fungamyl® and BAN® (Novo Nordisk). The enzymes may be of anysuitable origin, such as vegetable, animal, bacterial, fungal and yeastorigin. Amylase enzymes are normally incorporated in the detergentcomposition at levels from 0.0001% to 2%, preferably from about 0.0001%to about 0.5%, more preferably from about 0.0005% to about 0.1%, evenmore preferably from about 0.001% to about 0.05% of active enzyme byweight of the detergent composition.

Amylase enzymes also include those described in WO95/26397 and inco-pending application by Novo Nordisk PCT/DK96/00056. Other specificamylase enzymes for use in the detergent compositions of the presentinvention therefore include:

α-amylases characterised by having a specific activity at least 25%higher than the specific activity of Termamyl® at a temperature range of25° C. to 55° C. and at a pH value in the range of 8 to 10, measured bythe Phadebas® α-amylase activity assay. as described at pages 9–10,WO95/26397; and variants of amylase as described. in the patentapplication PCT/DK96/00056.

Other amylases suitable herein include, for example, α-amylasesdescribed in GB 1,296,839 to Novo; RAPIDASE®, InternationalBio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo isespecially useful. Engineering of enzymes for improved stability, e.g.,oxidative stability, is known. See, for example J. Biological Chem.,Vol. 260, No. 11, June 1985, pp. 6518–6521. Certain preferredembodiments of the present compositions can make use of amylases havingimproved stability in detergents such as automatic dishwashing types,especially improved oxidative stability as measured against areference-point of TERMAMYL® in commercial use in 1993. These preferredamylases herein share the characteristic of being “stability-enhanced”amylases, characterized, at a minimum, by a measurable improvement inone or more of: oxidative stability, e.g., to hydrogenperoxide/tetraacetylethylenediamine in buffered solution at pH 9–10;thermal stability, e.g., at common wash temperatures such as about 60°C.; or alkaline stability, e.g., at a pH from about 8 to about 11,measured versus the above-identified reference-point amylase. Stabilitycan be measured using any of the art-disclosed technical tests. See, forexample, references disclosed in WO 9402597. Stability-enhanced amylasescan be obtained from Novo or from Genencor International. One class ofhighly preferred amylases herein have the commonality of being derivedusing site-directed mutagenesis from one or more of the Bacillusamylases, especially the Bacillus α-amylases, regardless of whether one,two or multiple amylase strains are the immediate precursors. Oxidativestability-enhanced amylases vs. the above-identified reference amylaseare preferred for use, especially in bleaching, more preferably oxygenbleaching, as distinct from chlorine bleaching, detergent compositionsherein. Such preferred amylases include (a) an amylase according to thehereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as furtherillustrated by a mutant in which substitution is made, using alanine orthreonine, preferably threonine, of the methionine residue located inposition 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®,or the homologous position variation of a similar parent amylase, suchas B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b)stability-enhanced amylases as described by Genencor International in apaper entitled “Oxidatively Resistant alpha-Amylases” presented at the207th American Chemical Society National Meeting, Mar. 13–17, 1994, byC. Mitchinson. Therein it was noted that bleaches in automaticdishwashing detergents inactivate alpha-amylases but that improvedoxidative stability amylases have been made by Genencor from B.licheniformis NCIB8061. Methionine (Met) was identified as the mostlikely residue to be modified. Met was substituted, one at a time, inpositions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants,particularly important being M197L and M197T with the M197T variantbeing the most stable expressed variant. Stability was measured inCASCADE® and SUNLIGHT®; (c) particularly preferred amylases hereininclude amylase variants having additional modification in the immediateparent as described in WO 9510603 A and are available from the assignee,Novo, as DURAMYL®. Other particularly preferred oxidative stabilityenhanced amylase include those described in WO 9418314 to GenencorInternational and WO 9402597 to Novo. Any other oxidativestability-enhanced amylase can be used, for example as derived bysite-directed mutagenesis from known chimeric, hybrid or simple mutantparent forms of available amylases. Other preferred enzyme modificationsare accessible. See WO 9509909 A to Novo.

Various carbohydrase enzymes which impart antimicrobial activity mayalso be included in the present invention. Such enzymes includeendoglycosidase, Type II endoglycosidase and glucosidase as disclosed inU.S. Pat. Nos. 5,041,236, 5,395,541, 5,238,843 and 5,356,803 thedisclosures of which are herein incorporated by reference. Of course,other enzymes having antimicrobial activity may be employed as wellincluding peroxidases, oxidases and various other enzymes.

It is also possible to include an enzyme stabilization system into thecompositions of the present invention when any enzyme is present in thecomposition.

Perfumes—Perfumes and perfumery ingredients useful in the presentmethods comprise a wide variety of natural and synthetic chemicalingredients, including, but not limited to, aldehydes, ketones, esters,and the like. Also included are various natural extracts and essenceswhich can comprise complex mixtures of ingredients, such as orange oil,lemon oil, rose extract, lavender, musk, patchouli, balsamic essence,sandalwood oil, pine oil, cedar, and the like. Finished perfumes cancomprise extremely complex mixtures of such ingredients. Finishedperfumes typically comprise from about 0.01% to about 2%, by weight, ofthe detergent compositions herein, and individual perfumery ingredientscan comprise from about 0.0001% to about 90% of a finished perfumecomposition.

Non-limiting examples of perfume ingredients useful herein include:7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;ionone methyl; ionone gamma methyl; methyl cedrylone; methyldihydrojasmonate; methyl 1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone;benzophenone; methyl beta-naphthyl ketone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal,4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecane; condensation products ofhydroxycitronellal and methyl anthranilate, condensation products ofhydroxycitronellal and indol, condensation products of phenylacetaldehyde and indol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin;heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin;decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acidlactone;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;beta-naphthol methyl ether; ambroxane;dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1b]furan; cedrol,5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenylacetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl)cyclohexyl acetate.

Particularly preferred perfume materials are those that provide thelargest odor improvements in finished product compositions containingcellulases. These perfumes include but are not limited to: hexylcinnamic aldehyde; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate;beta-napthol methyl ether; methyl beta-naphthyl ketone;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane;dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; anisaldehyde;coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenylacetate; and tricyclodecenyl propionate.

Other perfume materials include essential oils, resinoids, and resinsfrom a variety of sources including, but not limited to: Peru balsam,Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoinresin, coriander and lavandin. Still other perfume chemicals includephenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol,nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzyl acetate, andeugenol. Carriers such as diethylphthalate can be used in the finishedperfume compositions.

Chelating Agents—The detergent compositions used in the methods hereinmay also optionally contain one or more iron and/or manganese chelatingagents. Such chelating agents can be selected from the group consistingof amino carboxylates, amino phosphonates, polyfunctionally-substitutedaromatic chelating agents and mixtures therein, all as hereinafterdefined. Without intending to be bound by theory, it is believed thatthe benefit of these materials is due in part to their exceptionalability to remove iron and manganese ions from washing solutions byformation of soluble chelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetrace-tates, N-hydroxyethylethylenediaminetriacetates,nitrilo-tri-acetates, ethylenediamine tetrapro-prionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldi-glycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate (“EDDS”), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycinediacetic acid (MGDA) salts (or acid form) as a chelant or co-builder.Similarly, the so called “weak” builders such as citrate can also beused as chelating agents.

If utilized, these chelating agents will generally comprise from about0.1% to about 15% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

Composition pH—The compositions used in the methods of the inventionwill be subjected to acidic stresses created by soils, such as food,when put to use, i.e., diluted and applied to soiled dishes. If acomposition with a pH greater than 7 is to be more effective, itpreferably should contain a buffering agent capable of providing agenerally more alkaline pH in the composition and in dilute solutions,i.e., about 0.1% to 0.4% by weight aqueous solution, of the composition.The pK_(a) value of this buffering agent should be about 0.5 to 1.0 pHunits below the desired pH value of the composition (determined asdescribed above). Preferably, the pK_(a) of the buffering agent shouldbe from about 7 to about 10. Under these conditions the buffering agentmost effectively controls the pH while using the least amount thereof.

The buffering agent may be an active detergent in its own right, or itmay be a low molecular weight, organic or inorganic material that isused in this composition solely for maintaining an alkaline pH.Preferred buffering agents for compositions of this invention arenitrogen-containing materials. Some examples are amino acids such aslysine or lower alcohol amines like mono-, di-, and tri-ethanolamine.Other preferred nitrogen-containing buffering agents areTri(hydroxymethyl)amino methane (HOCH₂)₃CNH₃ (TRIS),2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-propanol,2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyldiethanolamide, 1,3-diamino-propanolN,N′-tetra-methyl-1,3-diamino-2-propanol, N,N-bis(2-hydroxyethyl)glycine(bicine) and N-tris (hydroxymethyl)methyl glycine (tricine). Mixtures ofany of the above are also acceptable. Useful inorganicbuffers/alkalinity sources include the alkali metal carbonates andalkali metal phosphates, e.g., sodium carbonate, sodium polyphosphate.For additional buffers see McCutcheon's EMULSIFIERS AND DETERGENTS,North American Edition, 1997, McCutcheon Division, MC Publishing CompanyKirk and WO 95/07971 both of which are incorporated herein by reference.

The buffering agent, if used, is present in the compositions of theinvention herein at a level of from about 0.1% to 15%, preferably fromabout 1% to 10%, most preferably from about 2% to 8%, by weight of thecomposition.

Calcium and/or Magnesium Ions—For LDL compositions the presence ofcalcium and/or magnesium (divalent) ions improves the cleaning of greasysoils for various compositions, i.e., compositions containing alkylethoxy sulfates and/or polyhydroxy fatty acid amides. This is especiallytrue when the compositions are used in softened water that contains fewdivalent ions. It is believed that calcium and/or magnesium ionsincrease the packing of the surfactants at the oil/water interface,thereby reducing interfacial tension and improving grease cleaning.

Compositions used in the methods of the invention herein containingmagnesium and/or calcium ions exhibit good grease removal, manifestmildness to the skin, and provide good storage stability. These ions maybe optionally present in the compositions herein at an active level offrom about 0.1% to 4%, preferably from about 0.3% to 3.5%, morepreferably from about 0.5% to 1%, by weight.

Preferably, the magnesium or calcium ions are added as a hydroxide,chloride, acetate, formate, oxide or nitrate salt to the compositions ofthe present invention. Calcium ions may also be added as salts of thehydrotrope.

The amount of calcium or magnesium ions present in compositions of theinvention will be dependent upon the amount of total surfactant presenttherein. When calcium ions are present in the compositions of thisinvention, the molar ratio of calcium ions to total anionic surfactantshould be from about 0.25:1 to about 2:1.

Formulating such divalent ion-containing compositions in alkaline pHmatrices may be difficult due to the incompatibility of the divalentions, particularly magnesium, with hydroxide ions. When both divalentions and alkaline pH are combined with the surfactant mixture of thisinvention, grease cleaning is achieved that is superior to that obtainedby either alkaline pH or divalent ions alone. Yet, during storage, thestability of these compositions becomes poor due to the formation ofhydroxide precipitates. Therefore, chelating agents discussedhereinbefore may also be necessary.

Other Ingredients—The detergent compositions used in the methods of thepresent invention may further preferably comprise one or more detersiveadjuncts selected from the following: soil release polymers, polymericdispersants, polysaccharides, abrasives, bactericides, tarnishinhibitors, builders, enzymes, opacifiers, dyes, buffers, antifungal ormildew control agents, insect repellents, perfumes, hydrotropes,thickeners, processing aids, suds boosters, brighteners, anti-corrosiveaids, stabilizers antioxidants and chelants. A wide variety of otheringredients useful in detergent compositions can be included in thecompositions herein, including other active ingredients, carriers,hydrotropes, antioxidants, processing aids, dyes or pigments, solventsfor liquid formulations, solid fillers for bar compositions, etc. Ifhigh sudsing is desired, suds boosters such as the C₁₀–C₁₆ alkanolamidescan be incorporated into the compositions, typically at 1%–10% levels.The C₁₀–C₁₄ monoethanol and diethanol amides illustrate a typical classof such suds boosters. Use of such suds boosters with high sudsingadjunct surfactants such as the amine oxides, betaines and sultainesnoted above is also advantageous.

An antioxidant can be optionally added to the detergent compositions ofthe present invention. They can be any conventional antioxidant used indetergent compositions, such as 2,6-di-tert-butyl-4-methylphenol (BHT),carbamate, ascorbate, thiosulfate, monoethanolamine (MEA),diethanolamine, triethanolamine, etc. It is preferred that theantioxidant, when present, be present in the composition from about0.001% to about 5% by weight.

Various detersive ingredients employed in the present compositionsoptionally can be further stabilized by absorbing said ingredients ontoa porous hydrophobic substrate, then coating said substrate with ahydrophobic coating. Preferably, the detersive ingredient is admixedwith a surfactant before being absorbed into the porous substrate. Inuse, the detersive ingredient is released from the substrate into theaqueous washing liquor, where it performs its intended detersivefunction.

To illustrate this technique in more detail, a porous hydrophobic silica(trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzymesolution containing 3%–5% of C₁₃₋₁₅ ethoxylated alcohol (EO 7) nonionicsurfactant. Typically, the enzyme/surfactant solution is 2.5× the weightof silica. The resulting powder is dispersed with stirring in siliconeoil (various silicone oil viscosities in the range of 500–12,500 can beused). The resulting silicone oil dispersion is emulsified or otherwiseadded to the final detergent matrix. By this means, ingredients such asthe aforementioned enzymes, bleaches, bleach activators, bleachcatalysts, photoactivators, dyes, fluorescers, fabric conditioners andhydrolyzable surfactants can be “protected” for use in detergents,including liquid laundry detergent compositions.

Further, these hand dishwashing detergent embodiments preferably furthercomprises a hydrotrope. Suitable hydrotropes include sodium, potassium,ammonium or water-soluble substituted ammonium salts of toluene sulfonicacid, naphthalene sulfonic acid, cumene sulfonic acid, xylene sulfonicacid.

The detergent compositions of this invention can be in any form,including granular, paste, gel or liquid. Highly preferred embodimentsare in liquid or gel form. Liquid detergent compositions can containwater and other solvents as carriers. Low molecular weight primary orsecondary alcohols exemplified by methanol, ethanol, propanol, andisopropanol are suitable. Monohydric alcohols are preferred forsolubilizing surfactant, but polyols such as those containing from 2 toabout 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g.,1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) canalso be used. The compositions may contain from 5% to 90%, typically 10%to 50% of such carriers.

An example of the procedure for making granules of the detergentcompositions herein is as follows:—Linear aklylbenzenesulfonate, citricacid, sodium silicate, sodium sulfate perfume, diamine and water areadded to, heated and mixed via a crutcher. The resulting slurry is spraydried into a granular form.

An example of the procedure for making liquid detergent compositionsherein is as follows:—To the free water and citrate are added anddissolved. To this solution amine oxide, betaine, ethanol, hydrotropeand nonionic surfactant are added. If free water isn't available, thecitrate are added to the above mix then stirred until dissolved. At thispoint, an acid is added to neutralize the formulation. It is preferredthat the acid be chosen from organic acids such as maleic and citric,however, inorganic mineral acids may be employed as well. In preferredembodiments these acids are added to the formulation followed by diamineaddition. AExS is added last.

Non-Aqueous Liquid Detergents

The manufacture of liquid detergent compositions which comprise anon-aqueous carrier medium can be prepared according to the disclosuresof U.S. Pat. Nos. 4,753,570; 4,767,558; 4,772,413; 4,889,652; 4,892,673;GB-A-2,158,838; GB-A-2,195,125; GB-A-2,195,649; U.S. Pat. No. 4,988,462;U.S. Pat. No. 5,266,233; EP-A-225,654 (Jun. 16, 1987); EP-A-510,762(Oct. 28, 1992); EP-A-540,089 (May 5, 1993); EP-A-540,090 (May 5, 1993);U.S. Pat. No. 4,615,820; EP-A-565,017 (Oct. 13, 1993); EP-A-030,096(Jun. 10, 1981), incorporated herein by reference. Such compositions cancontain various particulate detersive ingredients stably suspendedtherein. Such non-aqueous compositions thus comprise a LIQUID PHASE and,optionally but preferably, a SOLID PHASE, all as described in moredetail hereinafter and in the cited references.

The compositions of this invention can be used to form aqueous washingsolutions for use hand dishwashing. Generally, an effective amount ofsuch compositions is added to water to form such aqueous cleaning orsoaking solutions. The aqueous solution so formed is then contacted withthe dishware, tableware, flatware and cooking utensils.

An effective amount of the detergent compositions herein added to waterto form aqueous cleaning solutions can comprise amounts sufficient toform from about 500 to 20,000 ppm of composition in aqueous solution.More preferably, from about 800 to 5,000 ppm of the detergentcompositions herein will be provided in aqueous cleaning liquor.

Personal Cleansing compositions

The compositions used in the methods of the present invention may alsobe a personal cleansing composition. That is a composition for directapplication to a persons, skin, hair etc. Examples of personal cleansingcompositions includes, but is not limited to, body washes, facialscrubs, shampoos, conditions, medicated shampoos, anti-dandruffshampoos, so-called 2-in-1 shampoos and conditioners, toilet bars, handsoap (including liquid or bar), deodorant soap, and the like.

The conventional personal cleansing composition used in the methods ofthe present invention additionally contains a conventional personalcleansing additive. The conventional personal cleansing additive ispresent from about 0.001% to about 49.9% by weight. Preferably, theconventional personal cleansing additive will be present from at leastabout 0.5%, more preferably, at least about 1%, even more preferably atleast about 2%, by weight. Additionally, the conventional personalcleansing additives can also be present at least about 5%, at leastabout 8% and at least about 10%, by weight but it is more preferablethat the conventional personal cleansing additive be present in at leastabout 2% by weight. Furthermore, the conventional personal cleansingadditive will be preferably present in the personal cleansingcomposition at preferably at less than about 45%, more preferably lessthan about 40%, even more preferably less than about 35%, even morepreferably less than about 30%, even more preferably less than about20%, by weight. This conventional personal cleansing additive isselected from the group comprising;

-   -   a) conditioning agent    -   b) conventional personal care polymer;    -   c) antidandruff agent    -   d) cosurfactant; and    -   e) mixtures thereof.

These conventional personal cleansing additives are just some of thepossible ingredients which can be conventionally added to personalcleansing compositions.

The conditioning agents, (a), useful in the present invention can befurther selected from the group comprising

-   -   1) non-volatile hydrocarbons conditioning agents;    -   2) silicone conditioning agents; and    -   3) mixtures thereof.

The conventional personal care polymers, (b), useful in the presentinvention can be further selected from the group comprising

-   -   i) deposition polymers;    -   ii) styling polymers and solvent;    -   iii) dispersed phase polymers; and    -   iv) mixtures thereof.        a) Conditioning Agent

The personal cleansing compositions used in the methods of the presentinvention comprise from about 0.005% to about 20%, preferably from about0.01% to about 10%, more preferably from about 0.1% to about 5%, andeven more preferably from about 0.5% to about 3% of dispersed particlesof a nonvolatile hair or skin conditioning agent. Suitable hair or skinconditioning agents include nonvolatile silicone conditioning agents,nonvolatile hydrocarbon conditioning agents, and mixtures thereof.

As used herein, average particle size of the conditioning agentparticles may be measured within the personal cleansing compositions bylight scattering methods well known in the art for determining averageparticle size for emulsified liquids. One such method involves the useof a Horiba LA-910 particle size analyzer.

For more information and additional examples of conditioning agents seecopending U.S. patent application Ser. No. 08/733,046, Attorney docketNo 6303 filed on Oct. 16, 1996 and U.S. patent application Ser. No.08/738,156, Attorney docket No 6331 filed on Oct. 25, 1996. See also U.SPat. No. 4,741,855. All three of these references are incorporatedherein by reference.

1) Nonvolatile Silicone Conditioning Agents—Preferred conditioningagents useful herein include nonvolatile, dispersed siliconeconditioning agents. By nonvolatile is meant that the siliconeconditioning agent exhibits very low or no significant vapor pressure atambient conditions, e.g., 1 atmosphere at 25° C. The nonvolatilesilicone conditioning agent preferably has a boiling point at ambientpressure of above about 250° C., preferably of above about 260° C., andmore preferably of above about 275° C. By dispersed is meant that theconditioning agent forms a separate, discontinuous phase from theaqueous carrier such as in the form of an emulsion or a suspension ofdroplets.

The nonvolatile silicone hair conditioning agents suitable for useherein preferably have a viscosity of from about 1,000 to about2,000,000 centistokes at 25° C., more preferably from about 10,000 toabout 1,800,000, and even more preferably from about 100,000 to about1,500,000. The viscosity can be measured by means of a glass capillaryviscometer as set forth in Dow Corning Corporate Test Method CTM0004,Jul. 20, 1970, which is incorporated by reference herein in itsentirety. Suitable silicone fluids include polyalkyl siloxanes, polyarylsiloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, andmixtures thereof. Other nonvolatile silicones having hair conditioningproperties can also be used.

The silicones herein also include polyalkyl or polyaryl siloxanes withthe following structure:

wherein R is alkyl or aryl, and x is an integer from about 7 to about8,000. “A” represents groups which block the ends of the siliconechains. The alkyl or aryl groups substituted on the siloxane chain (R)or at the ends of the siloxane chains (A) can have any structure as longas the resulting silicone remains fluid at room temperature, isdispersible, is neither irritating, toxic nor otherwise harmful whenapplied to the hair, is compatible with the other components of thecomposition, is chemically stable under normal use and storageconditions, and is capable of being deposited on and conditions thehair. Suitable A groups include hydroxy, methyl, methoxy, ethoxy,propoxy, and aryloxy. The two R groups on the silicon atom may representthe same group or different groups. Preferably, the two R groupsrepresent the same group. Suitable R groups include methyl, ethyl,propyl, phenyl, methylphenyl and phenylmethyl. The preferred siliconesare polydimethyl siloxane, polydiethylsiloxane, andpolymethylphenylsiloxane. Polydimethylsiloxane, which is also known asdimethicone, is especially preferred. The polyalkylsiloxanes that can beused include, for example, polydimethylsiloxanes. These silicones areavailable, for example, from the General Electric Company in theirViscasilR and SF 96 series, and from Dow Corning in their Dow Corning200 series.

Polyalkylaryl siloxane fluids can also be used and include, for example,polymethylphenylsiloxanes. These siloxanes are available, for example,from the General Electric Company as SF 1075 methyl phenyl fluid or fromDow Corning as 556 Cosmetic Grade Fluid.

Especially preferred, for enhancing the shine characteristics of hair,are highly arylated silicones, such as highly phenylated polyethylsilicone having refractive indices of about 1.46 or higher, especiallyabout 1.52 or higher. When these high refractive index silicones areused, they should be mixed with a spreading agent, such as a surfactantor a silicone resin, as described below to decrease the surface tensionand enhance the film forming ability of the material.

The silicones that can be used include, for example, a polypropyleneoxide modified polydimethylsiloxane although ethylene oxide or mixturesof ethylene oxide and propylene oxide can also be used. The ethyleneoxide and polypropylene oxide level should be sufficiently low so as notto interfere with the dispersibility characteristics of the silicone.These material are also known as dimethicone copolyols.

Other silicones include amino substituted materials. Suitable alkylaminosubstituted silicones include those represented by the followingstructure (II)

wherein x and y are integers which depend on the molecular weight, theaverage molecular weight being approximately between 5,000 and 10,000.This polymer is also known as “amodimethicone”.

Suitable cationic silicone fluids include those represented by theformula (III)(R₁)_(a)G_(3-a)-Si—(—OSiG₂)_(n)-(—OSiG_(b)(R₁)_(2-b)m)—O—SiG_(3-a)(R₁)_(a)in which G is chosen from the group consisting of hydrogen, phenyl, OH,C₁–C₈ alkyl and preferably methyl; a denotes 0 or an integer from 1 to3, and preferably equals 0; b denotes 0 or 1 and preferably equals 1;the sum n+m is a number from 1 to 2,000 and preferably from 50 to 150, nbeing able to denote a number from 0 to 1,999 and preferably from 49 to149 and m being able to denote an integer from 1 to 2,000 and preferablyfrom 1 to 10; R₁ is a monovalent radical of formula C_(q)H_(2q)L inwhich q is an integer from 2 to 8 and L is chosen from the groups—N(R₂)CH₂—CH₂—N(R₂)₂—N(R₂)₂—N(R₂)₃A⁻—N(R₂)CH₂—CH₂—NR₂H₂A⁻in which R₂ is chosen from the group consisting of hydrogen, phenyl,benzyl, a saturated hydrocarbon radical, preferably an alkyl radicalcontaining from 1 to 20 carbon atoms, and A⁻ denotes a halide ion.

An especially preferred cationic silicone corresponding to formula (III)is the polymer known as “trimethylsilylamodimethicone”, of formula (IV):

In this formula n and m are selected depending on the exact molecularweight of the compound desired.

Other silicone cationic polymers which can be used in the personalcleansing compositions are represented by the formula (V):

where R³ denotes a monovalent hydrocarbon radical having from 1 to 18carbon atoms, preferably an alkyl or alkenyl radical such as methyl; R₄denotes a hydrocarbon radical, preferably a C₁–C₁₈ alkylene radical or aC₁–C₁₈, and more preferably C₁–C₈, alkyleneoxy radical; Q⁻ is a halideion, preferably chloride; r denotes an average statistical value from 2to 20, preferably from 2 to 8; s denotes an average statistical valuefrom 20 to 200, and preferably from 20 to 50. A preferred polymer ofthis class is available from Union Carbide under the name “UCAR SILICONEALE 56.”

References disclosing suitable silicones include U.S. Pat. No.2,826,551, to Geen; U.S. Pat. No. 3,964,500, to Drakoff, issued Jun. 22,1976; U.S. Pat. No. 4,364,837, to Pader; and British Patent No. 849,433,to Woolston, all of which are incorporated herein by reference in theirentirety. Also incorporated herein by reference in its entirety is“Silicon Compounds” distributed by Petrarch Systems, Inc., 1984. Thisreference provides an extensive, though not exclusive, listing ofsuitable silicones.

Another silicone hair conditioning material that can be especiallyuseful is a silicone gum. The term “silicone gum”, as used herein, meansa polyorganosiloxane material having a viscosity at 25° C. of greaterthan or equal to 1,000,000 centistokes. It is recognized that thesilicone gums described herein can also have some overlap with theabove-disclosed silicones. This overlap is not intended as a limitationon any of these materials. Silicone gums are described by Petrarch, Id.,and others including U.S. Pat. No. 4,152,416, to Spitzer et al., issuedMay 1, 1979 and Noll, Walter, Chemistry and Technology of Silicones, NewYork: Academic Press 1968. Also describing silicone gums are GeneralElectric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE76. All of these described references are incorporated herein byreference in their entirety. The “silicone gums” will typically have amass molecular weight in excess of about 200,000, generally betweenabout 200,000 and about 1,000,000. Specific examples includepolydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane)copolymer, poly(dimethylsiloxane) (diphenylsiloxane)(methylvinylsiloxane) copolymer and mixtures thereof.

Also useful are silicone resins, which are highly crosslinked polymericsiloxane systems. The crosslinking is introduced through theincorporation of trifunctional and tetrafunctional silanes withmonofunctional or difunctional, or both, silanes during manufacture ofthe silicone resin. As is well understood in the art, the degree ofcrosslinking that is required in order to result in a silicone resinwill vary according to the specific silane units incorporated into thesilicone resin. In general, silicone materials which have a sufficientlevel of trifunctional and tetrafunctional siloxane monomer units, andhence, a sufficient level of crosslinking, such that they dry down to arigid, or hard, film are considered to be silicone resins. The ratio ofoxygen atoms to silicon atoms is indicative of the level of crosslinkingin a particular silicone material. Silicone materials which have atleast about 1.1 oxygen atoms per silicon atom will generally be siliconeresins herein. Preferably, the ratio of oxygen:silicon atoms is at leastabout 1.2:1.0. Silanes used in the manufacture of silicone resinsinclude monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-,methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, andtetrachlorosilane, with the methyl-substituted silanes being mostcommonly utilized. Preferred resins are offered by General Electric asGE SS4230 and SS4267. Commercially available silicone resins willgenerally be supplied in a dissolved form in a low viscosity volatile ornonvolatile silicone fluid. The silicone resins for use herein should besupplied and incorporated into the present compositions in suchdissolved form, as will be readily apparent to those skilled in the art.Without being limited by theory, it is believed that the silicone resinscan enhance deposition of other silicones on the hair and can enhancethe glossiness of hair with high refractive index volumes.

Other useful silicone resins are silicone resin powders such as thematerial given the CTFA designation polymethylsilsequioxane, which iscommercially available as Tospearl™ from Toshiba Silicones.

Background material on silicones, including sections discussing siliconefluids, gums, and resins, as well as the manufacture of silicones, canbe found in Encyclopedia of Polymer Science and Engineering, Volume 15,Second Edition, pp 204–308, John Wiley & Sons, Inc., 1989, which isincorporated herein by reference in its entirety.

Silicone materials and silicone resins in particular, can convenientlybe identified according to a shorthand nomenclature system well known tothose skilled in the art as the “MDTQ” nomenclature. Under this system,the silicone is described according to the presence of various siloxanemonomer units which make up the silicone. Briefly, the symbol M denotesthe monofunctional unit (CH₃)₃SiO_(0.5); D denotes the difunctional unit(CH₃)₂SiO; T denotes the trifunctional unit (CH₃)SiO_(1.5); and Qdenotes the quadri- or tetra-functional unit SiO₂. Primes of the unitsymbols, e.g., M′, D′, T′, and Q′ denote substituents other than methyl,and must be specifically defined for each occurrence. Typical alternatesubstituents include groups such as vinyl, phenyl, amino, hydroxyl, etc.The molar ratios of the various units, either in terms of subscripts tothe symbols indicating the total number of each type of unit in thesilicone, or an average thereof, or as specifically indicated ratios incombination with molecular weight, complete the description of thesilicone material under the MDTQ system. Higher relative molar amountsof T, Q, T′ and/or Q′ to D, D′, M and/or or M′ in a silicone resin isindicative of higher levels of crosslinking. As discussed before,however, the overall level of crosslinking can also be indicated by theoxygen to silicon ratio.

The silicone resins for use herein which are preferred are MQ, MT, MTQ,MQ and MDTQ resins. Thus, the preferred silicone substituent is methyl.Especially preferred are MQ resins wherein the M:Q ratio is from about0.5:1.0 to about 1.5:1.0 and the average molecular weight of the resinis from about 1000 to about 10,000.

2) Nonvolatile Hydrocarbon Conditioning Agents—Other suitable hairconditioning agents suitable for use in the personal cleansingcomposition include nonvolatile organic conditioning agents. Suitablenonvolatile organic conditioning agents for use in the composition arethose conditioning agents that are known or otherwise effective for useas hair or skin conditioning agent.

The nonvolatile hydrocarbons for use in the personal cleansingcomposition may be saturated or unsaturated, and may be straight, cyclicor branched chain. By nonvolatile is meant that the hydrocarbonconditioning agent exhibits very low or no significant vapor pressure atambient conditions, e.g., 1 atmosphere at 25° C. The nonvolatilehydrocarbon agent preferably has a boiling point at ambient pressure ofabove about 250° C., preferably above about 260° C., and more preferablyof above about 275° C. The nonvolatile hydrocarbons preferably have fromabout 12 to about 40 carbon atoms, more preferably from about 12 toabout 30 carbon atoms, and most preferably from about 12 to about 22carbon atoms. Also encompassed herein are polymeric hydrocarbons ofalkenyl monomers, such as polymers of C₂–C₁₂ alkenyl monomers, including1-alkenyl monomers such as polyalphaolefin monomers. These polymers canbe straight or branched chain polymers. The straight chain polymers willtypically be relatively short in length, having a total number of carbonatoms as described above in this paragraph. The branched chain polymerscan have substantially higher chain lengths. Also useful herein are thevarious grades of mineral oils. Mineral oils are liquid mixtures ofhydrocarbons that are obtained from petroleum.

Specific examples of suitable nonvolatile hydrocarbons include, but arenot limited to, paraffin oil, mineral oil, dodecane, isododecane,hexadecane, isohexadecane, eicosene, isoeicosene, tridecane,triglyceride oils, tetradecane, polyoctene, polydecene, polydodecene,products of polymerization of mixtures of C₂₋₁₂ monomers, for examplethe polymer produced by the polymerization of polyoctene, polydecene andpolydodecene, and mixtures thereof. Isododecane, isohexadeance, andisoeicosene are commercially available as Permethyl 99A, Permethyl 101A,and Permethyl 1082, from Presperse, South Plainfield, N.J. A copolymerof isobutene and normal butene is commercially available as IndopolH-100 from Amoco Chemicals. Preferred among these hydrocarbons aremineral oil, isododecane, isohexadecane, polybutene, polyisobutene, andmixtures thereof.

Optional Suspending Agent—The personal cleansing compositions used inthe methods of the present invention may further comprise a suspendingagent at concentrations effective for suspending the optionalconditioning agent, or other water-insoluble material, in dispersed formin the personal cleansing compositions. Such concentrations range fromabout 0.1% to about 10%, preferably from about 0.5% to about 5.0%, byweight of the personal cleansing compositions.

Optional suspending agents include crystalline suspending agents thatcan be categorized as acyl derivatives, long chain amine oxides, orcombinations thereof, concentrations of which range from about 0.3% toabout 5.0%, preferably from about 0.5% to about 3.0%, by weight of thepersonal cleansing compositions. When used in the personal cleansingcompositions, these suspending agents are present in crystalline form.These suspending agents are described in U.S. Pat. No. 4,741,855, whichdescription is incorporated herein by reference. These preferredsuspending agents include ethylene glycol esters of fatty acidspreferably having from about 16 to about 22 carbon atoms. More preferredare the ethylene glycol stearates, both mono and distearate, butparticularly the distearate containing less than about 7% of the monostearate. Other suitable suspending agents include alkanol amides offatty acids, preferably having from about 16 to about 22 carbon atoms,more preferably about 16 to 18 carbon atoms, preferred examples of whichinclude stearic monoethanolamide, stearic diethanolamide, stearicmonoisopropanolamide and stearic monoethanolamide stearate. Other longchain acyl derivatives include long chain esters of long chain fattyacids (e.g., stearyl stearate, cetyl palmitate, etc.); glyceryl esters(e.g., glyceryl distearate) and long chain esters of long chain alkanolamides (e.g., stearamide diethanolamide distearate, stearamidemonoethanolamide stearate). Long chain acyl derivatives, ethylene glycolesters of long chain carboxylic acids, long chain amine oxides, andalkanol amides of long chain carboxylic acids in addition to thepreferred materials listed above may be used as suspending agents. Forexample, it is contemplated that suspending agents with long chainhydrocarbyls having C₈–C₂₂ chains may be used.

Other long chain acyl derivatives suitable for use as suspending agentsinclude N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof(e.g., Na, K), particularly N,N-di(hydrogenated) C₁₆, C₁₈ and tallowamido benzoic acid species of this family, which are commerciallyavailable from Stepan Company (Northfield, Ill., USA).

Examples of suitable long chain amine oxides for use as suspendingagents include alkyl (C₁₆–C₂₂) dimethyl amine oxides, e.g., stearyldimethyl amine oxide

Other suitable suspending agents include xanthan gum at concentrationsranging from about 0.3% to about 3%, preferably from about 0.4% to about1.2%, by weight of the personal cleansing compositions. The use ofxanthan gum as a suspending agent in silicone containing personalcleansing compositions is described, for example, in U.S. Pat. No.4,788,006, which description is incorporated herein by reference.Combinations of long chain acyl derivatives and xanthan gum may also beused as a suspending agent in the personal cleansing compositions. Suchcombinations are described in U.S. Pat. No. 4,704,272, which descriptionis incorporated herein by reference.

Other suitable suspending agents include carboxyvinyl polymers.Preferred among these polymers are the copolymers of acrylic acidcrosslinked with polyallylsucrose as described in U.S. Pat. No.2,798,053, which description is incorporated herein by reference.Examples of these polymers include Carbopol 934, 940, 941, and 956,available from B. F. Goodrich Company.

Other suitable suspending agents include primary amines having a fattyalkyl moiety having at least about 16 carbon atoms, examples of whichinclude palmitamine or stearamine, and secondary amines having two fattyalkyl moieties each having at least about 12 carbon atoms, examples ofwhich include dipalmitoylamine or di(hydrogenated tallow)amine. Stillother suitable suspending agents include di(hydrogenated tallow)phthalicacid amide, and crosslinked maleic anhydride-methyl vinyl ethercopolymer.

Other suitable suspending agents may be used in the personal cleansingcompositions, including those that can impart a gel-like viscosity tothe composition, such as water soluble or colloidally water solublepolymers like cellulose ethers (e.g., methylcellulose, hydroxybutylmethylcellulose, hyroxypropylcellulose, hydroxypropyl methylcellulose,hydroxyethyl ethylcellulose and hydorxethylcellulose), guar gum,polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starchand starch derivatives, and other thickeners, viscosity modifiers,gelling agents, etc. Mixtures of these materials can also be used.

b) Conventional Personal Care Polymer:

The personal cleansing compositions used in the methods of the presentinvention comprise from about 0.01% to about 20%, preferably from about0.05% to about 10%, more preferably from about 0.1% to about 5%, andeven more preferably from about 0.1% to about 3% of a conventionalpersonal care polymer. Suitable conventional personal care polymersinclude:

-   -   i) deposition polymers;    -   ii) styling polymers and solvent;    -   iii) dispersed phase polymers; and    -   iv) mixtures thereof.        i) Deposition Polymer—The personal cleansing compositions used        in the methods of the present invention can additionally        comprise an organic deposition polymer as a deposition aid. It        can be present at levels of from about 0.01 to about 5%,        preferably from about 0.05 to about 1%, more preferably from        about 0.08% to about 0.5% by weight. The polymer may be a        homopolymer or be formed from two or more types of monomers. The        molecular weight of the polymer will generally be between about        25,000 and about 10,000,000, preferably between about 100,000        and about 5,000,000, more preferably in the range between about        300,000 to about 3,000,000 and most preferably from about        500,000 to about 2,000,000. Preferably the deposition polymer is        a cationic polymer and preferably will have cationic nitrogen        containing groups such as quaternary ammonium or protonated        amino groups, or a mixture thereof. It is preferred that when        the deposition polymer is present there is additionally present        in the composition a hair conditioning agent, antidandruff        agent, styling polymer or mixtures thereof, all of which are        defined hereafter. Alternatively the deposition polymer can be        used independantly, that is on its own, in the personal        cleansing composition.

See copending U.S. patent application Ser. Nos. 07/960,473, Ser. No.08/738,156, filed on Oct. 25, 1996, 60/053,319, filed on Jul. 21, 1997,all of which are incorporated herein by reference, for exemplificationof deposition polymers.

The cationic charge density has been found to need to be at least 0.1meq/g, preferably above 0.5 and most preferably above 0.8 or higher. Thecationic charge density should not exceed 5 meq/g, it is preferably lessthan 3 and more preferably less than 2 meq/g. The charge density can bemeasured using the Kjeldahl method and should be within the above limitsat the desired pH of use, which will in general be from about 3 to 9 andpreferably between 4 and 8.

The concentration of the deposition polymer in the personal cleansingwhen it is a cationic polymer is preferably from about 0.025% to about3%, more preferably from about 0.05% to about 2%, even more preferablyfrom about 0.1% to about 1%, by weight of the personal cleansingcomposition.

Any anionic counterions can be use in association with the cationicpolymers so long as the polymers remain soluble in water, in thepersonal cleansing composition, or in a coacervate phase of the personalcleansing composition, and so long as the counterions are physically andchemically compatible with the essential components of the personalcleansing composition or do not otherwise unduly impair productperformance, stability or aesthetics. Non limiting examples of suchcounterions include halides (e.g., chlorine, fluorine, bromine, iodine),sulfate and methylsulfate.

The cationic nitrogen-containing moiety of the cationic polymer isgenerally present as a substituent on all, or more typically on some, ofthe monomer units thereof. Thus, the cationic polymer for use in thepersonal cleansing composition includes homopolymers, copolymers,terpolymers, and so forth, of quaternary ammonium or cationicamine-substituted monomer units, optionally in combination withnon-cationic monomers referred to herein as spacer monomers. Nonlimiting examples of such polymers are described in the CTFA CosmeticIngredient Dictionary, 3rd edition, edited by Estrin, Crosley, andHaynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc.,Washington, D.C. (1982)), which description is incorporated herein byreference.

Suitable cationic polymers include, for example, copolymers of vinylmonomers having cationic amine or quaternary ammonium functionalitieswith water soluble spacer monomers such as (meth)acrylamide, alkyl anddialkyl (meth)acrylamides, alkyl (meth)acrylate, vinyl caprolactone andvinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferablyhave C1–C7 alkyl groups, more preferably C1–C3 alkyl groups. Othersuitable spacers include vinyl esters, vinyl alcohol, maleic anhydride,propylene glycol and ethylene glycol.

The cationic amines can be primary, secondary or tertiary amines,depending upon the particular species and the pH of the personalcleansing. In general secondary and tertiary amines, especiallytertiary, are preferred.

Amines substituted vinyl monomers and amines can be polymerized in theamine form and then converted to ammonium by quaternization.

Suitable cationic amino and quaternary ammonium monomers include, forexample, vinyl compounds substituted with dialkyl aminoalkyl acrylate,dialkylamino alkylmethacrylate, monoalkylaminoalkyl acrylate,monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammoniumsalt, trialkyl acryloxyalkyl ammonium sale, diallyl quaternary ammoniumsalts, and vinyl quaternary ammonium monomers having cyclic cationicnitrogen-containing rings such as pyridinium, imidazolium, andquaternized pyrrolidine, e.g., alkyl vinyl imidazolium, and quaternizedpyrrolidine, e.g., alkyl vinyl imidazolium, alkyl vinyl pyridinium,alkyl vinyl pyrrolidine salts. The alkyl portions of these monomers arepreferably lower alkyls such as the C₁–C₃ alkyls, more preferably C₁ andC₂ alkyls.

Suitable amine-substituted vinyl monomers for use herein includedialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate,dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide,wherein the alkyl groups are preferably C₁–C₇ hydrocarbyls, morepreferably C₁–C₃ alkyls.

The cationic polymers hereof can comprise mixtures of monomer unitsderived from amine-and/or quaternary ammonium-substituted monomer and/orcompatible spacer monomers.

Suitable cationic deposition polymers include, for example: copolymersof 1-vinyl-2-pyrrolidine and 1-vinyl-3-methyl-imidazolium salt (e.g.,Chloride salt) (referred to in the industry by the Cosmetic, Toiletry,and Fragrance Association, “CTFA” as Polyquaternium-16) such as thosecommercially available from BASF Wyandotte Corp. (Parsippany, N.J., USA)under the LUVIQUAT tradename (e.g., LUVIQUAT FC 370); copolymers of1-vinyl-2-pyrrolidine and dimethylaminoethyl methacrylate (referred toin the industry by CTFA and Polyquaternium-11) such as thosecommercially from ISP Corporation (Wayne, N.J., USA) under the GAFQUATtradename (e.g., GAFQAT 755N); cationic diallyl quaternaryammonium-containing polymers including, for example,dimethyldiallyammonium chloride homopolymer and copolymers of acrylamideand dimethyldiallyammonium chloride, referred to in the industry (CTFA)as Polyquaternium 6 and Polyquaternium 7, respectively; and mineral acidsalts of amino-alkyl esters of homo-and co-polymers of unsaturatedcarboxylic acids having from 3 to 5 carbon atoms, as described in U.S.Pat. No. 4,009,256, incorporated herein by reference.

Other cationic polymers that can be used include polysaccharidepolymers, such as cationic cellulose derivatives and cationic starchderivatives. Cationic polysaccharide polymer materials suitable for useherein include those of the formula:

wherein: A is an anhydroglucose residual group, such as starch orcellulose anhydroglucose residual, R is an alkylene oxyalklene,polyoxyalkylene, or hydroxyalkylene group, or combination thereof, R¹,R² and R³ independently are alkyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18carbon atoms, and the total number of carbon atoms for each cationicmoiety (i.e., the sum of carbon atoms in R¹, R² and R³) preferably beingabout 20 or less, and X is an anionic counterion, as previouslydescribed.

Cationic cellulose is available from Amerchol Corp. (Edison, N.J., USA)in their Polymer JR (trademark) and LR (trade mark) series of polymers,as salts of hydroxyethyl cellulose reacted with trimethyl ammoniumsubstituted epoxide, referred to in the industry (CTFA) asPolyquaternium 10. Another type of cationic cellulose includes thepolymeric quaternary ammonium salts of hydroxyethyl cellulose reactedwith lauryl dimethyl ammonium-substituted epoxide, referred to in theindustry (CTFA) as Polyquaternium 24. These materials are available fromAmerchol Corp. (Edison, N.J., USA) under the tradename Polymer LM-200.

Other cationic polymers that can be used include cationic guar gumderivatives, such as guar hydroxypropyltrimonium chloride (commerciallyavailable from Celanese Corp. in their Jaguar trade mark series). Othermaterials include quaternary nitrogen-containing cellulose ethers (e.g.,as described in U.S. Pat. No. 3,962,418, incorporated by referenceherein), and copolymers of etherified cellulose and starch (e.g., asdescribed in U.S. Pat. No. 3,958,581, incorporated by reference herein).

The deposition polymer does not have to be soluble in the personalcleansing composition. Preferably, however, the cationic polymer iseither soluble in the personal cleansing composition, or in a complexcoacervate phase in the personal cleansing composition formed by thecationic polymer and anionic material. Complex coacervates of thecationic polymer can be formed with anionic surfactants or with anionicpolymers that can optionally be added to the composition hereof (e.g.,sodium polystyrene sulfonate).

Coacervate formation is dependent upon a variety of criteria such asmolecular weight, concentration, and ratio of interacting ionicmaterials, ionic strength (including modification of ionic strength, forexample, by addition of salts), charge density of the cationic andanionic species, pH, and temperature. Coacervate systems and the effectof these parameters have been described, for example, by J. Caelles, etal., “Anionic and Cationic Compounds in Mixed Systems”, Cosmetics &Toiletries, Vol. 106, April 1991, pp 49–54, C. J. van Oss,“Coacervation, Complex-Coacervation and Flocculation”, J. DispersionScience and Technology, Vol. 9 (5,6), 1988–89, pp 561–573, and D. J.Burgess, “Practical Analysis of Complex Coacervate Systems”, J. ofColloid and Interface Science, Vol. 140, No. 1, November 1990, pp227–238, which descriptions are incorporated herein by reference.

It is believe to be particularly advantageous for the cationic polymerto be present in the personal cleansing in a coacervate phase, or toform a coacervate phase upon application or rinsing of the personalcleansing to or from the hair. Complex coacervates are believed to morereadily deposit on the hair. Thus, in general, it is preferred that thecationic polymer exist in the personal cleansing as a coacervate phaseor form a coacervate phase upon dilution. If not already a coacervate inthe personal cleansing, the cationic polymer will preferably exist in acomplex coacervate form in the personal cleansing upon dilution withwater to a water:personal cleansing composition rate ratio of about20:1, more preferably at about 10:1, even more preferably at about 8:1.

Techniques for analysis of formation of complex coacervates are known inthe art. For example, microscopic analyses of the personal cleansingcompositions, at any chosen stage of dilution, can be utilized toidentify whether a coacervate phase has formed. Such coacervate phasewill be identifiable as an additional emulsified phase in thecomposition. The use of dyes can aid in distinguishing the coacervatephase from other insoluble phase dispersed in the composition.

Preferably the deposition polymer is selected from the group comprisingcationic hydroxyalkyl cellulose ethers and cationic guar derivatives.Particularly preferred deposition polymers are Jaguar C13S, Jaguar C15,Jaguar C17 and Jaguar C16 and Jaguar C162. Other preferred cationiccellulose ethers include Polymer JR400, JR30M and JR125.

Surfactant soluble Conditioning Oil—The shampoo compositions used in themethods of the present invention may additionally comprise a lowviscosity, surfactant soluble conditioning oil which is solubilized inthe surfactant component as an additional hair conditioning agent foruse in combination with the cationic hair conditioning polymer describedhereinbefore. The concentration of the low viscosity, surfactant solubleoil ranges from about 0.05% to about 3%, preferably from about 0.08% toabout 1.5%, more preferably from about 0.1% to about 1%, by weight ofthe shampoo composition.

The low viscosity, surfactant soluble, conditioning oils are waterinsoluble, water dispersible, liquids selected from the group consistingof hydrocarbon oils and fatty esters, or combinations thereof, whereinthe surfactant soluble conditioning oil has a viscosity of from about 1to about 300 centipoise, preferably from about 1 to about 150centipoise, more preferably from about 2 to about 50 centipoise, asmeasured at 40° C. according to ASTM D-445.

It has been found that these low viscosity surfactant solubleconditioning oils provide the shampoo composition with improvedconditioning performance when used in combination with the depositionpolymers described herein. These surfactant soluble conditioning oilsare believed to be solubilized in the surfactant micelles of the shampoocomposition. It is also believed that this solubilization into thesurfactant micelles contributes to the improved hair conditioningperformance of the shampoo compositions herein.

Suitable surfactant soluble conditioning oils for use in the shampoocomposition include hydrocarbon oils having at least about 10 carbonatoms, such as cyclic hydrocarbons, straight chain aliphatichydrocarbons (saturated or unsaturated), and branched chain aliphatichydrocarbons (saturated or unsaturated), including polymers thereof.Straight chain hydrocarbon oils preferably contain from about 12 toabout 19 carbon atoms. Branched chain hydrocarbon oils, includinghydrocarbon polymers, can and typically will contain more than 19 carbonatoms. Specific non limiting examples of these hydrocarbon oils includeparaffin oil, mineral oil, saturated and unsaturated dodecane, saturatedand unsaturated tridecane, saturated and unsaturated tetradecane,saturated and unsaturated pentadecane, saturated and unsaturatedhexadecane, polybutene, polydecene, and combinations thereof.Branched-chain isomers of these compounds, as well as of higher chainlength hydrocarbons, can also be used, examples of which include highlybranched, saturated or unsaturated, alkanes such as thepermethyl-substituted isomers, e.g., the permethyl-substituted isomersof hexadecane and eicosane, such as 2, 2, 4, 4, 6, 6, 8,8-dimethyl-10-methylundecane and 2, 2, 4, 4, 6,6-dimethyl-8-methylnonane, sold by Permethyl Corporation. Hydrocarbonpolymers such as polybutene and polydecene, especially polybutene, canalso be used.

Other surfactant soluble conditioning oils for use in the shampoocomposition include a liquid polyolefin such as a liquid polyalphaolefinor a hydrogenated liquid polyalphaolefin. Polyolefins suitable for usein the shampoo composition herein are prepared by polymerization ofolefenic monomers containing from about 4 to about 14 carbon atoms,preferably from about 6 to about 12 carbon atoms. Polyalphaolefins arepreferred, and are prepared by polymerization of 1-alkene monomershaving from about 4 to about 14 carbon atoms, preferably from about 6 toabout 12 carbon atoms.

Non limiting examples of olefenic monomers for use in preparing thepolyolefin liquids herein include ethylene, propylene, 1-butene,1-pentene, 1-hexene, 1-octene, 1decene, 1-dodecene, 1-tetradecene,branched chain isomers such as 4-methyl-1-pentene, and combinationsthereof. Also suitable for preparing the polyolefin liquids areolefin-containing refinery feedstocks or effluents. Preferred, however,are the hydrogenated alpha-olefin monomers having from about 4 to about14 carbon atoms, or combinations thereof, examples of which include1-hexene to 1-hexadecenes and combinations thereof, and preferably are1-octene to 1-tetradecene or combinations thereof.

(ii) Styling polymer—The personal cleansing compositions used in themethods of the present invention may additionally contain awater-insoluble hair styling polymer, concentrations of which range fromabout 0.1% to about 10%, preferably from about 0.3% to about 7%, morepreferably from about 0.5% to about 5%, by weight of the composition.These styling polymers provide the personal cleansing composition of thepresent invention with hair styling performance by providing a thinpolymeric film on the hair after application from a personal cleansingcomposition. The polymeric film deposited on the hair has adhesive andcohesive strength, as is understood by those skilled in the art. It isessential that when a styling polymer is present in the personalcleansing compositions of the invention that a solvent, definedhereafter, is also present in the It is preferred that when a stylingpolymer is present a deposition polymer be also present. Thiscombination improves deposition and retention of the styling polymer.Furthermore, it is preferd that when the personal cleansing compositioncontains a styling polymer it is preferred that a cationic spreadingagent be present.

Many such polymers are known in the art, including water-insolubleorganic polymers and water-insoluble silicone-grafted polymers, all ofwhich are suitable for use in the personal cleansing composition hereinprovided that they also have the requisite features or characteristicsdescribed hereinafter. Such polymers can be made by conventional orotherwise known polymerization techniques well known in the art, anexample of which includes free radical polymerization.

See copending U.S. patent application Ser. No. 08/738,211, filed on Oct.25, 1996 and Ser. No. 60/053,319, filed on Oct. 25, 1996 both of whichare incorporated herein by reference.

Examples of suitable organic and silicone grafted polymers for use inthe personal cleansing composition of the present invention aredescribed in greater detail hereinafter.

Organic styling polymer—The styling polymers suitable for use in themethods of the present invention include organic styling polymers wellknown in the art. The organic styling polymers may be homopolymers,copolymers, terpolymers or other higher polymers, but must comprise oneor more polymerizable hydrophobic monomers to thus render the resultingstyling polymer hydrophobic and water-insoluble as defined herein. Thestyling polymers may therefore further comprise other water soluble,hydrophilic monomers provided that the resulting styling polymers havethe requisite hydrophobicity and water insolubility.

As used herein, the term “hydrophobic monomer” refers to polymerizableorganic monomers that can form with like monomers a water-insolublehomopolymer, and the term “hydrophilic monomer” refers to polymerizableorganic monomers that can form with like monomers a water-solublehomopolymer.

The organic styling polymers preferably have a weight average molecularweight of at least about 20,000, preferably greater than about 25,000,more preferably greater than about 30,000, most preferably greater thanabout 35,000. There is no upper limit for molecular weight except thatwhich limits applicability of the invention for practical reasons, suchas processing, aesthetic characteristics, formulateability, etc. Ingeneral, the weight average molecular weight will be less than about10,000,000, more generally less than about 5,000,000, and typically lessthan about 2,000,000. Preferably, the weight average molecular weightwill be between about 20,000 and about 2,000,000, more preferablybetween about 30,000 and about 1,000,000, and most preferably betweenabout 40,000 and about 500,000.

The organic styling polymers also preferably have a glass transitiontemperature (Tg) or crystalline melting point (Tm) of at least about−20° C., preferably from about 20° C. to about 80° C., more preferablyfrom about 20° C. to about 60° C. Styling polymers having these Tg or Tmvalues form styling films on hair that are not unduly sticky or tacky tothe touch. As used herein, the abbreviation “Tg” refers to the glasstransition temperature of the backbone of the polymer, and theabbreviation “Tm” refers to the crystalline melting point of thebackbone, if such a transition exists for a given polymer. Preferably,both the Tg and the Tm, if any, are within the ranges recitedhereinabove.

The organic styling polymers are carbon chains derived frompolymerization of hydrophobic monomers such as ethylenically unsaturatedmonomers, cellulosic chains or other carbohydrate-derived polymericchains. The backbone may comprise ether groups, ester groups, amidegroups, urethanes, combinations thereof, and the like.

The organic styling polymers may further comprise one or morehydrophilic monomers in combination with the hydrophobic monomersdescribed herein, provided that the resulting styling polymer has therequisite hydrophobic character and water-insolubility. Suitablehydrophilic monomers include, but are not limited to, acrylic acid,methacrylic acid, N,N-dimethylacrylamide, dimethyl aminoethylmethacrylate, quaternized dimethylaminoethyl methacrylate,methacrylamide, N-t-butyl acrylamide, maleic acid, maleic anhydride andits half esters, crotonic acid, itaconic acid, acrylamide, acrylatealcohols, hydroxyethyl methacrylate, diallyldimethyl ammonium chloride,vinyl pyrrolidone, vinyl ethers (such as methyl vinyl ether),maleimides, vinyl pyridine, vinyl imidazole, other polar vinylheterocyclics, styrene sulfonate, allyl alcohol, vinyl alcohol (such asthat produced by the hydrolysis of vinyl acetate after polymerization),salts of any acids and amines listed above, and mixtures thereof.Preferred hydrophilic monomers include acrylic acid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, vinyl pyrrolidone, salts of acids and amineslisted above, and combinations thereof.

Suitable hydrophobic monomers for use in the organic styling polymerinclude, but are not limited to, acrylic or methacrylic acid esters ofC₁–C₁₈ alcohols, such as methanol, ethanol, methoxy ethanol, 1-propanol,2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol,3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol,1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol,t-butanol(2-methyl-2-propanol), cyclohexanol, neodecanol,2-ethyl-1-butanol, 3-heptanol, benzyl alcohol, 2-octanol,6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol,3,5,5-tri methyl-1-hexanol, 1-decanol, 1-dodecanol, 1-hexadecanol,1-octa decanol, and the like, the alcohols having from about 1 to about18 carbon atoms, preferably from about 1 to about 12 carbon atoms;styrene; polystyrene macromer; vinyl acetate; vinyl chloride; vinylidenechloride; vinyl propionate; alpha-methylstyrene; t-butylstyrene;butadiene; cyclohexadiene; ethylene; propylene; vinyl toluene; andmixtures thereof. Preferred hydrophobic monomers include n-butylmethacrylate, isobutyl methacrylate, t-butyl acrylate, t-butylmethacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, vinylacetate, and mixtures thereof, more preferably t-butyl acrylate, t-butylmethacrylate, or combinations thereof.

The styling polymers for use in the personal cleansing compositionpreferably comprise from about 20% to 100%, more preferably from about50% to about 100%, even more preferably from about 60% to about 100%, byweight of the hydrophobic monomers, and may further comprise from zeroto about 80% by weight of hydrophilic monomers. The particular selectionand combination of monomers for incorporation into the styling polymerwill help determine its formulational properties. By appropriateselection and combination of, for example, hydrophilic and hydrophobicmonomers, the styling polymer can be optimized for physical and chemicalcompatibility with the selected styling polymer solvent describedhereinafter and other components of the personal cleansing composition.The selected monomer composition of the organic styling polymer must,however, render the styling polymer water-insoluble but may be solublein the selected solvent described hereinafter. In this context, theorganic styling polymer is soluble in the solvent if the organic polymeris solubilized in the solvent at 25° C. at the polymer and solventconcentrations of the personal cleansing formulation selected. However,a solution of the organic styling polymer and solvent may be heated tospeed up solubility of the styling polymer in the solvent. Such stylingpolymer and solvent formulation, including the selection of monomers foruse in the styling polymer, to achieve the desired solubility is wellwithin the skill of one in the art.

Examples of preferred organic styling polymers include t-butylacrylate/2-ethylhexyl acrylate copolymers having a weight/weight ratioof monomers of about 95/5, about 90/10, about 80/20, about 70/30, about60/40, and about 50/50; t-butyl acrylate/2-ethylhexyl methacrylatecopolymers having a weight/weight ratio of monomers of about 95/5, about90/10, about 80/20, about 70/30, about 60/40, and about 50/50; t-butylmethacrylate/2-ethylhexyl acrylate copolymers having a weight/weightratio of monomers of about 95/5, about 90/10, about 80/20, about 70/30,about 60/40, and about 50/50; t-butyl methacrylate/2-ethylhexylmethacrylate copolymers having a weight/weight ratio of monomers ofabout 95/5, about 90/10, about 80/20, about 70/30, about 60/40, andabout 50/50; t-butyl ethacrylate/2-ethylhexyl methacrylate copolymershaving a weight/weight ratio of monomers of about 95/5, about 90/10,about 80/20, about 70/30, about 60/40, and about 50/50; vinylpyrrolidone/vinyl acetate copolymers having a weight/weight ratio ofmonomers of about 10/90, and about 5/95; and mixtures thereof.

Especially preferred polymers are t-butyl acrylate/2-ethylhexylmethacrylate copolymers having a weight/weight ratio of monomers ofabout 95/5, about 90/10, about 80/20, about 70/30, about 60/40, andabout 50/50; t-butyl methacrylate/2-ethylhexyl methacrylate copolymershaving a weight/weight ratio of monomers of about 95/5, about 90/10,about 80/20, about 70/30, about 60/40, and about 50/50; and mixturesthereof.

Examples of other suitable styling polymers are described in U.S. Pat.No. 5,120,531, to Wells et al., issued Jun. 9, 1992; U.S. Pat. No.5,120,532, to Wells et al., issued Jun. 9, 1992; U.S. Pat. No.5,104,642, to Wells et al., issued Apr. 14, 1992; U.S. Pat. No.4,272,511, to Papantoniou et al., issued Jun. 9, 1981; U.S. Pat. No.4,963,348, to Bolich et al., issued Oct. 16, 1990 and U.S. Pat. No.4,196,190, to Gehman et al., issued Apr. 1, 1980, which descriptions areincorporated herein by reference.

Silicone-grafted styling polymer—Other suitable styling polymers for usein the methods of the present invention are silicone-grafted hairstyling resins. These polymers may be used alone or in combination withthe organic styling polymers described hereinbefore. Many such polymerssuitable for use in the personal cleansing composition herein are knownin the art. These polymers are characterized by polysiloxane moietiescovalently bonded to and pendant from a polymeric carbon-based backbone.

The backbone of the silicone-grafted polymer is preferably a carbonchain derived from polymerization of ethylenically unsaturated monomers,but can also be cellulosic chains or other carbohydrate-derivedpolymeric chains to which polysiloxane moieties are pendant. Thebackbone can also include ether groups, ester groups, amide groups,urethane groups and the like. The polysiloxane moieties can besubstituted on the polymer or can be made by co-polymerization ofpolysiloxane-containing polymerizable monomers (e.g. ethylenicallyunsaturated monomers, ethers, and/or epoxides) withnon-polysiloxane-containing polymerizable monomers.

The silicone-grafted styling polymers for use in the personal cleansingcomposition comprise “silicone-containing” (or“polysiloxane-containing”) monomers, which form the silicone macromerpendant from the backbone, and non-silicone-containing monomers, whichform the organic backbone of the polymer. That is a siloxane monomergrafted to the hair styling polymer.

Preferred silicone-grafted polymers comprise an organic backbone,preferably a carbon backbone derived from ethylenically unsaturatedmonomers, such as a vinyl polymeric backbone, and a polysiloxanemacromer (especially preferred are polydialkylsiloxane, most preferablypolydimethylsiloxane) grafted to the backbone. The polysiloxane macromershould have a weight average molecular weight of at least about 500,preferably from about 1,000 to about 100,000, more preferably from about2,000 to about 50,000, most preferably about 5,000 to about 20,000.Organic backbones contemplated include those that are derived frompolymerizable, ethylenically unsaturated monomers, including vinylmonomers, and other condensation monomers (e.g., those that polymerizeto form polyamides and polyesters), ring-opening monomers (e.g., ethyloxazoline and caprolactone), etc. Also contemplated are backbones basedon cellulosic chains, ether-containing backbones, etc.

Preferred silicone grafted polymers for use in the personal cleansingcomposition comprise monomer units derived from: at least one freeradically polymerizable ethylenically unsaturated monomer or monomersand at least one free radically polymerizable polysiloxane-containingethylenically unsaturated monomer or monomers.

The silicone grafted polymers suitable for use in the personal cleansingcomposition generally comprise from about 1% to about 50%, by weight, ofpolysiloxane-containing monomer units and from about 50% to about 99% byweight, of non-polysiloxane-containing monomers. Thenon-polysiloxane-containing monomer units can be derived from thehydrophilic and/or hydrophobic monomer units described hereinbefore.

The styling polymer for use in the personal cleansing composition cantherefore comprise combinations of the hydrophobic and/orpolysiloxane-containing monomer units described herein, with or withouthydrophilic comonomers as described herein, provided that the resultingstyling polymer has the requisite characteristics as described herein.

Suitable polymerizable polysiloxane-containing monomers include, but arenot limited to, those monomers that conform to the formula:X(Y)_(n)Si(R)_(3-m)Z_(m)wherein X is an ethylenically unsaturated group copolymerizable with thehydrophobic monomers described herein, such as a vinyl group; Y is adivalent linking group; R is a hydrogen, hydroxyl, lower alkyl (e.g.C₁–C₄), aryl, alkaryl, alkoxy, or alkylamino; Z is a monovalent siloxanepolymeric moiety having a number average molecular weight of at leastabout 500, which is essentially unreactive under copolymerizationconditions, and is pendant from the vinyl polymeric backbone describedabove; n is 0 or 1; and m is an integer from 1 to 3. These polymerizablepolysiloxane-containing monomers have a weight average molecular weightas described above.

A preferred polysiloxane-containing monomer conforms to the formula:

wherein m is 1, 2 or 3 (preferably m=1); p is 0 or 1; q is an integerfrom 2 to 6; R¹ is hydrogen, hydroxyl, lower alkyl, alkoxy, alkylamino,aryl, or alkaryl (preferably R¹ is alkyl); X conforms to the formula

wherein R² is hydrogen or —COOH (preferably R² is hydrogen); R³ ishydrogen, methyl or —CH₂COOH (preferably R³ is methyl); Z conforms tothe formula:

wherein R⁴, R⁵, and R⁶ independently are lower alkyl, alkoxy,alkylamino, aryl, arylalkyl, hydrogen or hydroxyl (preferably R⁴, R⁵,and R⁶ are alkyls); and r is an integer of about 5 or higher, preferablyabout 10 to about 1500 (most preferably r is from about 100 to about250). Most preferably, R⁴, R⁵, and R⁶ are methyl, p=0, and q=3.

Another preferred polysiloxane monomer conforms to either of thefollowing formulas

wherein: s is an integer from 0 to about 6, preferably 0, 1, or 2, morepreferably 0 or 1; m is an integer from 1 to 3, preferably 1; R² isC1–C10 alkyl or C7–C10 alkylaryl, preferably C1–C6 alkyl or C7–C10alkylaryl, more preferably C1–C2 alkyl; n is an integer from 0 to 4,preferably 0 or 1, more preferably 0.

The silicone grafted styling polymers suitable for use in the personalcleansing composition preferably comprise from about 50% to about 99%,more preferably from about 60% to about 98%, most preferably from about75% to about 95%, by weight of the polymer, of non-siliconemacromer-containing monomer units, e.g. the total hydrophobic andhydrophilic monomer units described herein, and from about 1% to about50%, preferably from about 2% to about 40%, more preferably from about5% to about 25%, of silicone macromer-containing monomer units, e.g. thepolysiloxane-containing monomer units described herein. The level ofhydrophilic monomer units can be from about 0% to about 70%, preferablyfrom about 0% to about 50%, more preferably from about 0% to about 30%,most preferably from about 0% to about 15%; the level of hydrophobicmonomer units, can be from 30% to about 99%, preferably from about 50%to about 98%, more preferably from about 70% to about 95%, mostpreferably from about 85% to about 95%.

Examples of some suitable silicone grafted polymers for use in thepersonal cleansing composition herein are listed below. Each listedpolymer is followed by its monomer composition as weight part of monomerused in the synthesis:

-   -   (i)        t-butylacrylatye/t-butyl-methacrylate/2-ethylhexyl-methacrylate/PDMS        macromer-20,000 molecular weight macromer 31/27/32/10    -   (ii) t-butylmethacrylate/2-ethylhexyl-methacrylate/PDMS        macromer-15,000 molecular weight macromer 75/10/15    -   (iii) t-butylmethacrylate/2-ethylhexyl-acrylate/PDMS        macromer-10,000 molecular weight macromer 65/15/20    -   (iv) t-butylacrylate/2-ethylhexyl-acrylate/PDMS macromer-14,000        molecular weight macromer 77/11/12    -   (v) t-butylacrylate/2-ethylhexyl-methacrylate/PDMS        macromer-13,000 molecular weight macromer 81/9/10

Examples of other suitable silicone grafted polymers for use in thepersonal cleansing composition of the present invention are described inEPO Application 90307528.1, published as EPO Application 0 408 311 A2 onJan. 11, 1991, Hayama, et al.; U.S. Pat. No. 5,061,481, issued Oct. 29,1991, Suzuki et al.; U.S. Pat. No. 5,106,609, Bolich et al., issued Apr.21, 1992; U.S. Pat. No. 5,100,658, Bolich et al., issued Mar. 31, 1992;U.S. Pat. No. 5,100,657, Ansher-Jackson, et al., issued Mar. 31, 1992;U.S. Pat. No. 5,104,646, Bolich et al., issued Apr. 14, 1992; U.S. Ser.No. 07/758,319, Bolich et al, filed Aug. 27, 1991, U.S. Ser. No.07/758,320, Torgerson et al., filed Aug. 27, 1991, which descriptionsare incorporated herein by reference.

Solvent—The personal cleansing composition used in the methods of thepresent invention must additionally comprise a volatile solvent forsolubilizing the styling polymers, described hereinbefore, when such astyling polymer is present. The solvent helps disperse the stylingpolymer as water-insoluble fluid particles throughout the personalcleansing composition, wherein the dispersed particles comprise thestyling polymer and the volatile solvent. Solvents suitable for thispurpose include hydrocarbons, ethers, esters, amines, alkyl alcohols,volatile silicone derivatives and combinations thereof, many examples ofwhich are well known in the art.

The volatile solvent must be water-insoluble or have a low watersolubility. The selected styling polymer, however, must also besufficiently soluble in the selected solvent to allow dispersion of thehair styling polymer and solvent combination as a separate, dispersedfluid phase in the personal cleansing composition.

The solvent suitable for use in the personal cleansing composition mustalso be a volatile material. In this context, the term volatile meansthat the solvent has a boiling point of less than about 300° C.,preferably from about 90° C. to about 260° C., more preferably fromabout 100° C. to about 200° C. (at about one atmosphere of pressure).

The concentration of the volatile solvent in the personal cleansingcomposition must be sufficient to solubilize the hair styling polymerand disperse it as a separate fluid phase in the personal cleansingcomposition. Such concentrations generally range from about 0.10% toabout 10%, preferably from about 0.5% to about 8%, most preferably fromabout 1% to about 6%, by weight of the personal cleansing composition,wherein the weight ratio of styling polymer to solvent is preferablyfrom about 10:90 to about 70:30, more preferably from about 20:80 toabout 65:35, even more preferably from about 30:70 to about 60:40. Ifthe weight ratio of styling polymer to solvent is too low, the latheringperformance of the personal cleansing composition is negativelyaffected. If the ratio of polymer to solvent is too high, thecomposition becomes too viscous and causes difficulty in the dispersionof the styling polymer. The hair styling agents should have an averageparticle diameter in the final personal cleansing product of from about0.05 to about 100 microns, preferably from about 0.2 micron to about 25microns. Particle size can be measured according to methods known in theart, including, for example optical microscopy.

Preferred volatile solvents for use in the personal cleansingcomposition are the hydrocarbon solvents, especially branched chainhydrocarbon solvents. The hydrocarbon solvents may be linear orbranched, saturated or unsaturated, hydrocarbons having from about 8 toabout 18 carbon atoms, preferably from about 10 to about 16 carbonatoms. Saturated hydrocarbons are preferred, as are branchedhydrocarbons. Nonlimiting examples of some suitable linear hydrocarbonsinclude decane, dodecane, decene, tridecene, and combinations thereof.Suitable branched hydrocarbons include isoparaffins, examples of whichinclude commercially available isoparaffins from Exxon Chemical Companysuch as Isopar H and K (C₁–C₁₂ isoparaffins), and Isopar L (C₁₁–C₁₃isoparaffins). Preferred branched hydrocarbons are isohexadecane,isododecane, 2,5-dimethyl decane, isotetradecane, and combinationsthereof. Commercially available branched hydrocarbons include Permethyl99A and 101A (available from Preperse, Inc., South Plainfield, N.J.,USA).

Other suitable solvents include isopropanol, butyl alcohol, amylalcohol, phenyl ethanol, benzyl alcohol, phenyl propanol, ethylbutyrate, isopropyl butyrate, diethyl phthalate, diethyl malonate,diethyl succinate, dimethyl malonate, dimethyl succinate, phenyl ethyldimethyl carbinol, ethyl-6-acetoxyhexanoate, and methyl(2-pentanyl-3-oxy)cyclopentylacetate, and mixtures thereof. Preferredamong such other suitable solvents are diethyl phthalate, diethylmalonate, diethyl succinate, dimethyl malonate, dimethyl succinate,phenylethyl dimethyl carbinol, ethyl-6-acetoxyhexanoate, and mixturesthereof.

Suitable ether solvents are the di(C₅–C₇) alkyl ethers and diethers,especially the di(C₅–C₆) alkyl ethers such as isoamyl ether, dipentylether and dihexyl ether.

Other suitable solvents for use in the personal cleansing compositionthe volatile silicon derivatives such as cyclic or linearpolydialkylsiloxane, linear siloxy compounds or silane. The number ofsilicon atoms in the cyclic silicones is preferably from about 3 toabout 7, more preferably about 3 to about 5.

The general formula for such silicones is:

wherein R₁ and R₂ are independently selected from C₁ to C₈ alkyl, arylor alkylaryl and wherein n=3–7. The linear polyorgano siloxanes havefrom about 2 to 7 silicon atoms and have the general formula:

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ can independently be saturatedor unsaturated C₁–C₈ alkyl, aryl, alkylaryl, hydroxyalkyl, amino alkylor alkyl siloxy.

Linear siloxy compounds have the general formula:

wherein R₁, R₂, R₃, R₄, R₅, and R₆ are independently selected fromsaturated or unsaturated C₁ to C₇ alkyl, aryl and alkyl aryl and R₇ isC₁ to C₄ alkylene.

Silane compounds have the general formula:

wherein R₁, R₂, R₃, and R₄ can independently be selected from C₁–C₈alkyl, aryl, alkylaryl, hydroxyalkyl and alkylsiloxy.

Silicones of the above type, both cyclic and linear, are offered by DowCorning Corporation, Dow Corning 344, 345 and 200 fluids, Union Carbide,Silicone 7202 and Silicone 7158, and Stauffer Chemical, SWS-03314.

The linear volatile silicones generally have viscosities of less thanabout 5 centistokes at 25° C. while the cyclic materials haveviscosities less than about 10 centistokes. Examples of volatilesilicones are described in Todd and Byers, “Volatile Silicone Fluids forCosmetics”, Cosmetics and Toiletries, Vol. 91, January, 1976, pp. 27–32,and also in Silicon Compounds, pages 253–295, distributed by PetrarchChemicals, which descriptions are incorporated herein by reference.

Cationic Spreading Agent—The personal cleansing compositions used in themethods of the present invention may additionally comprise selectcationic materials which act for use as spreading agents. The spreadingagents for use in the composition are select quaternary ammonium orprotonated amino compounds defined in greater detail hereinafter. Theseselect spreading agents are useful to improve spreadability of thewater-insoluble styling polymer on the body, for example on the hair.The concentration of the select spreading agents in the compositionrange from about 0.05% to about 5%, preferably from about 0.1% to about2%, more preferably from about 0.2% to about 1%, by weight of thepersonal cleansing composition.

It has been found that the select spreading agents will improvespreadability of a water-insoluble styling polymer when used in thepersonal cleansing composition of the present invention. In particular,the improved insoluble solvent, water-insoluble styling polymer, andcationic deposition polymer, are especially effective at improvingstyling performance of the composition. The improved styling performanceresults from the improved spreading efficiency of water-insolublestyling polymer attributed to the use of the select spreading agent inthe composition. onto hair. This improved spreading results in improvedstyling performance, or allows for formulation of the personal cleansingcomposition using reduced amounts of styling polymer or cationicdeposition polymer.

The select spreading agents are quaternary ammonium or amino compoundshaving 2, 3 or 4 N-radicals which are substituted or unsubstitutedhydrocarbon chains having from about 12 to about 30 carbon atoms,wherein the substituents includes nonionic hydrophilic moieties selectedfrom alkoxy, polyoxalkylene, alkylamido, hydroxyalkyl, alkylestermoieties, and mixtures thereof. Suitable hydrophile-containing radicalsinclude, for example, compounds having nonionic hydrophile moietiesselected from the group consisting of ethoxy, propoxy, polyoxyethylene,polyoxypropylene, ethylamido, propylamido, hydroxymethyl, hydroxyethyl,hydroxypropyl, methylester, ethylester, propylester, or mixturesthereof. The select spreading agents are cationic and must be positivelycharged at the pH of the personal cleansing compositions. Generally, thepH of the personal cleansing composition will be less than about 10,typically from about 3 to about 9, preferably from about 4 to about 8.

Select cationic spreading agents for use in the composition includethose corresponding to the to the formula:

wherein R₁, and R₂ are independently a saturated or unsaturated,substituted or unsubstituted, linear or branched hydrocarbon chainhaving from about 12 to about 30 carbon atoms, preferably from about 18to about 22 carbon atoms, and wherein the hydrocarbon chain can containone or more hydrophilic moieties selected from the alkoxy,polyoxyalkylene, alkylamido, hydroxyalkyl, alkylester, and mixturesthereof; R₃ and R₄ are independently a hydrogen, or a saturated orunsaturated, substituted or unsubstituted, linear or branchedhydrocarbon chain having from about 1 to about 30 carbon atoms, or ahydrocarbon having from about 1 to about 30 carbon atoms containing oneor more aromatic, ester, ether, amido, amino moieties present assubstitutents or as linkages in the chain, and wherein the hydrocarbonchain can contain one or more hydrophilic moieties selected from thealkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, alkylester, andmixtures thereof; and X is a soluble salt forming anion preferablyselected from halogen (especially chlorine), acetate, phosphate,nitrate, sulfonate, and alkylsulfate radicals.

An example of a select spreading agent for use in the compositioninclude those corresponding to the formula:

wherein n is from 10–28, preferably 16, and X is a water soluble saltforming anion (e.g., Cl, sulfate, etc.).

Other examples of select cationic spreading agents for use in thecomposition include those corresponding to the formula:

wherein Z₁ and Z₂ are independently saturated or unsaturated,substituted or unsubstituted, linear or branched hydrocarbons, andpreferably Z₁ is an alkyl, more preferably methyl, and Z₂ is a shortchain hydroxyalkyl, preferably hydroxymethyl or hydroxyethyl; n and mare independently integers from 1 to 4, inclusive, preferably from 2 to3, inclusive, more preferably 2; R′ and R″ are independently substitutedor unsubstituted hydrocarbons, preferably C₁₂–C₂₀ alkyl or alkenyl; andX is a soluble salt forming anion (e.g., Cl, sulfate, etc.).

Nonlimiting examples of suitable cationic spreading agents includeditallowdimethyl ammonium chloride, ditallowdimethyl ammonium methylsulfate, dihexadecyl dimethyl ammonium chloride, di-(hydrogenatedtallow) dimethyl ammonium chloride, dioctadecyl dimethyl ammoniumchloride, dieicosyl dimethyl ammonium chloride, didocosyl dimethylammonium chloride, di-(hydrogenated tallow) dimethyl ammonium acetate,dihexadecyl dimethyl ammonium acetate, ditallow dipropyl ammoniumphosphate, ditallow dimethyl ammonium nitrate, di-(coconutalkyl)dimethyl ammonium chloride, ditallowamidoethyl hydroxypropylmoniummethosulfate (commercially available as Varisoft 238), dihydrogenatedtallowamidoethyl hydroxyethylmonium methosulfate (commercially availableas Varisoft 110), ditallowamidoethyl hydroxyethylmonium methosulfate(commercially available as Varisoft 222), and di(partially hardenedsoyoylethyl) hydroxyethylmonium methosulfate (commercially available asArmocare EQ-S). Ditallowdimethyl ammonium chloride, ditallowamidoethylhydroxypropylmonium methosulfate, dihydrogenated tallowamidoethylhydroxyethylmonium methosulfate, ditallowamidoethyl hydroxyethylmoniummethosulfate, and di(partially hardened soyoylethyl) hydroxyethylmoniummethosulfate are particularly preferred quaternary ammonium cationicsurfactants useful herein.

Other suitable quaternary ammonium cationic surfactants are described inM.C. Publishing Co., McCutcheion's Detergents & Emulsifiers, (NorthAmerican edition 1979); Schwartz, et al., Surface Active Agents. TheirChemistry and Technology, New York: Interscience Publishers, 1949; U.S.Pat. No. 3,155,591, to Hilfer, issued Nov. 3, 1964; U.S. Pat. No.3,929,678 to Laughlin et al., issued Dec. 30, 1975; U.S. Pat. No.3,959,461 to Bailey et al, issued May 25, 1976; and U.S. Pat. No.4,387,090 to Bolich Jr., issued Jun. 7, 1983, which descriptions areincorporated herein by reference.

iii) Dispersed Phase Polymers

Another optional component of the personal cleansing compositions usedin the methods of the present invention is a dispersed phase polymer.Suitable dispersed phase polymers include water soluble nonionicpolymers and water soluble anionic polymers. Suitable nonionic polymersinclude cellulose ethers (e.g., hydroxybutyl methylcellulose,hydroxypropylcellulose, hydroxypropyl methylcellulose, ethylhydroxyethylcellulose and hydroxyethylcellulose), propylene glycol alginates,polyacrylamide, poly(ethylene oxide), polyvinyl alcohol,polyvinylpyrrolidone, hydroxypropyl guar gum, locust bean gum, amylose,hydroxyethyl amylose, starch and starch derivatives and mixturesthereof. Preferred nonionic polymers include hydroxyethyl cellulose,polyethylene oxide, polyvinyl pyrrolidone, polyvinyl alcohol,polyacrylamide, hydroxypropyl cellulose, ethylhydroxyethyl cellulose,dextran, polypropyleneoxide and hydroxypropyl guar or mixtures thereof.

Suitable anionic water-soluble polymers include carboxymethyl cellulose,carrageenan, xanthum gum polystyrene sulfonate, gum agar, gum ghatti,gum karaya, pectins, alginate salts, as well as poly(acrylic acid) andacrylic or methacrylic acid derivatives such as the alkali metal andammonium salts of acrylic acid, methacrylic acid. Mixtures of the aboveanionic water-soluble polymers may also be used.

These polymeric compositions may be homopolymers or they may becopolymers or terpolymers with other copolymerizing monomers known inthe art. Examples of copolymerizing monomers known in the art includebut are not limited to ethylene, propylene, isobutylene, styrene,polystyrene, alphamethylstyrene, vinyl acetate, vinyl formate, alkylethers, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidenechloride, the alkyl acrylates, the alkylmethacrylates, the alkylfumarates, the alkyl maleates, and other olefinic monomerscopolymerizable therewith as long as the resulting polymers are watersoluble and phase separate in the compositions of this invention.Copolymers of anionic and nonionic monomers such as acrylic acid andmethacrylic acid with acrylamide, methacrylamide, the N-alkylsubstituted amides, the N-aminoalkylamides, the correspondingN-alkylaminoalkyl substituted amides, the aminoalkyl acrylates, theaminoalkyl methacrylamides, and the N-alkyl substituted aminoalkylesters of either acrylic or methacrylic acids.

Preferred anionic polymers include polyacrylic acid; sodium carboxymethyl cellulose; polyacrylates; polymethyl acrylate; polysulphates suchas polyvinyl sulfate, polystyrene sulfonate, polyphosphates, sodiumdextran sulfate, alginate salts and pectate

When combined with the aqueous surfactant system and phase separationinitiator, described below, the water-soluble nonionic or anionicpolymer separates to form aqueous droplets suspended in a continuousaqueous phase. The number average particle size of the polymer dropletscan be from 0.1 microns to about 10,000 microns, preferably from about1.0 micron to about 5000 microns, most preferably from about 5 micronsto about 1000 microns.

Most preferred for use in the present invention are ethyl hydroxyethylcellulose, hydroxyethyl cellulose, hydroxypropyl guar and polystyrenesulfonate.

The herein described polymers are preferably present at a concentrationlevel of above about 0.1%, more preferably from about 0.15% to about10%, most preferably from about 0.2% to about 2%. mixtures of theanionic and nonionic water-soluble polymers may also be used.

See also copending U.S. patent application Ser. No. 08/786,521, Attorneydocket No 6484, which is incorporated herein by reference.

The personal care compositions of the invention when a dispersed phasepolymers is present preferably contain a phase separation initiator,defined herein after.

Phase Separation Initiators—The compositions used in the methods of thepresent invention may additionally contain a phase separation initiator.By the term “phase separation initiators”, as used herein, meanselectrolytes, amphiphiles or mixtures thereof capable of inducing phaseseparation when combined with compositions comprising a surfactantsystem and a nonionic or anionic water-soluble polymer.

By the term “amphiphile” as used herein, means, generally, substanceswhich contain both hydrophilic and hydrophobic (lipophilic) groups.Amphiphiles preferred for use in the present invention are those whichgenerally do not form micelles or liquid crystal phases and include, butare not limited to: amides of fatty acids; fatty alcohols; fatty esters,glycol mono- and di-esters of fatty acids; glyceryl esters.

Amides, including alkanol amides, are the condensation products of fattyacids with primary and secondary amines or alkanolamines to yieldproducts of the general formula:

wherein RCO is a fatty acid radical and R is C₈₋₂₀; X is an alkyl,aromatic or alkanol (CHR′CH₂OH wherein R′ is H or C₁₋₆ alkyl); Y is H,alkyl, alkanol or X. Suitable amides include, but are not limited to,cocamide, lauramide, oleamide and stearamide. Suitable alkanolamidesinclude, but are not limited to, cocamide DEA, cocamide MEA, cocamideMIPA, isostearamide DEA, isostearamide MEA, isostearamide MIPA,lanolinamide DEA, lauramide DEA, lauramide MEA, lauramide MIPA,linoleamide DEA, linoleamide MEA, linoleamide MIPA, myristamide DEA,myristamide MEA, myristamide MIPA, Oleamide DEA, Oleamide MEA, OleamideMIPA, palmamide DEA, palmamide MEA, palmamide MIPA, palmitamide DEA,palmitamide MEA, palm kernelamide DEA, palm kernelamide MEA, palmkernelamide MIPA, peanutamide MEA, peanutamide MIPA, soyamide DEA,stearamide DEA, stearamide MEA, stearamide MIPA, tallamide DEA,tallowamide DEA, tallowamide MEA, undecylenamide DEA, undecylenamideMEA. The condensation reaction may be carried out with free fatty acidsor with all types of esters of the fatty acids, such as fats and oils,and particularly methyl esters. The reaction conditions and the rawmaterial sources determine the blend of materials in the end product andthe nature of any impurities.

Fatty alcohols are higher molecular weight, nonvolatile, primaryalcohols having the general formula:RCH₂OHwherein R is a C₈₋₂₀ alkyl. They can be produced from natural fats andoils by reduction of the fatty acid COOH— grouping to the hydroxylfunction. Alternatively, identical or similarly structured fattyalcohols can be produced according to conventional synthetic methodsknown in the art. Suitable fatty alcohols include, but are not limitedto, behenyl alcohol, C₉₋₁₁ alcohols, C₁₂₋₁₃ alcohols, C₁₂₋₁₅ alcohols,C₁₂₋₁₆ alcohols, C₁₄₋₁₅ alcohols, caprylic alcohol, cetearyl alcohol,coconut alcohol, decyl alcohol, isocetyl alcohol, isostearyl alcohol,lauryl alcohol, oleyl alcohol, palm kernel alcohol, stearyl alcohol,cetyl alcohol, tallow alcohol, tridecyl alcohol or myristyl alcohol.

Glyceryl esters comprise a subgroup of esters which are primarily fattyacid mono- and di-glycerides or triglycerides modified by reaction withother alcohols and the like. Preferred glyceryl esters are mono anddiglycerides. Suitable glyceryl esters and derivatives thereof include,but are not limited to, acetylated hydrogenated tallow glyceride,glyceryl behenate, glyceryl caprate, glyceryl caprylate, glycerylcaprylate/caprate, glyceryl dilaurate, glyceryl dioleate, glycerylerucate, glyceryl hydroxystearate, glyceryl isostearate, glyceryllanolate, glyceryl laurate, glyceryl linoleate, glyceryl oleate,glyceryl stearate, glyceryl myristate, glyceryl distearate and mixturesthereof,

Also useful as amphiphiles in the present invention are long chainglycol esters or mixtures thereof. Included are ethylene glycol estersof fatty acids having from about 8 to about 22 carbon atoms. Fattyesters of the formula RCO—OR′ also act as suitable amphiphiles in thecompositions of the present invention, where one of R and R′ is a C₈₋₂₂alkyl and the other is a C₁₋₃ alkyl.

The amphiphiles of the present invention may also encompass a variety ofsurface active compounds such as nonionic and cationic surfactants. Ifincorporated into the compositions of the present invention, thesesurface active compounds become additional surfactants used asamphilphiles for the purpose of initiating phase separation and areseparate and apart from the surfactants of the surfactant system and thealkyl glyceryl sulfonate surfactant of the present invention.

Amphiphiles preferred for use herein include cocamide MEA, cetyl alcoholand stearyl alcohol.

The amphiphiles of the present invention are preferably present in thepersonal cleansing compositions at levels of from 0 to about 4%.preferably from about 0.5% to about 2%.

Suitable electrolytes include mono-, di- and trivalent inorganic saltsas well as organic salts. Surfactant salts themselves are not includedin the present electrolyte definition but other salts are. Suitablesalts include, but are not limited to, phosphates, sulfates, nitrates,citrates and halides. The counter ions of such salts can be, but are notlimited to, sodium, potassium, ammonium, magnesium or other mono-, diand tri valent cation. Electrolytes most preferred for use in thecompositions of the present invention include sodium chloride, ammoniumchloride, sodium citrate, and magnesium sulfate. It is recognized thatthese salts may serve as thickening aids or buffering aids in additionto their role as a phase separation initiator. The amount of theelectrolyte used will generally depend on the amount of the amphiphileincorporated, but may be used at concentration levels of from about 0.1%to about 4%, preferably from about 0.2% to about 2%.

The amount of phase separation initiator comprising the electrolyteand/or the amphiphile will vary with the type of surfactant and polymer,but is generally present at a level of from about 0.1% to about 5%,preferably from about 0.2% to about 3%.

In view of the essential nature and activity of the phase separationinitiators described above, the compositions of the present inventionare, preferably, substantially free of materials which would prevent theinduction or formation of separate, liquid phases. The term“substantially free”, as used here, means that the compositions of thepresent invention contain no more than about 0.5% of such materials,preferably less than 0.25%, more preferably zero. Such materialstypically include ethylene glycol, propylene glycol, ethyl alcohol andthe like.

The compositions of the present invention are also preferablysubstantially free of other ingredients which unduly minimize theformation of separate and distinct liquid phases, especially ingredientswhich do not provide a significant benefit to the present invention.

c) Antidandruff Agent

The personal cleansing compositions used in the methods of the presentinvention can additionally comprise a safe and effective amount of anantidandruff agent. The antidandruff agent provides the personalcleansing compositions with antidandruff activity. The antidandruffagent is preferably a crystalline particulate that is insoluble in, anddispersed throughout, the personal cleansing compositions. Effectiveconcentrations of such antidandruff agents generally range from about0.1% to about 5%, more preferably from about 0.3% to about 5%, by weightof the personal cleansing compositions.

See also U.S. Pat. No. 4,948,576 to Verdicchio et al, and copending U.S.patent application Ser. No. 08/738,211, filed on Oct. 25, 1996, Ser. No.08/622,222, filed on Mar. 27, 1996 and Ser. No. 08/593,727, all of whichare incorporated herein by reference.

Suitable antidandruff agents includes, for example, plateletpyridinethione salt crystal, octopirox, selenium sulfide, ketoconazoleand pyridinethione salts. Selenium sulfide is a preferred particulateantidandruff agent for use in the personal cleansing compositions,effective concentrations of which range from about 0.1% to about 5.0%,preferably from about 0.3% to about 2.5%, more preferably from about0.5% to about 1.5%, by weight of the personal cleansing compositions.Selenium sulfide is generally regarded as a compound having one mole ofselenium and two moles of sulfur, although it may also be a cyclicstructure, Se_(x)S_(y), wherein x+y=8. Average particle diameters forthe selenium sulfide (selenium disulfide) are less than 15 um,preferably less than 10 um, as measured by forward laser lightscattering device, e.g., Malvern 3600 instrument. Selenium sulfidecompounds are well known in the personal cleansing art, and aredescribed, for example in U.S. Pat. No. 2,694,668; U.S. Pat. No.3,152,046; U.S. Pat. No. 4,089,945; and U.S. Pat. No. 4,885,107, whichdescriptions are incorporated herein by reference.

Pyridinethione antidandruff agents, especially1-hydroxy-2-pyridinethione salts, are highly preferred particulateantidandruff agents for use in the personal cleansing compositions,concentrations of which range from about 0.1% to about 3%, preferablyabout 0.3% to about 2%, by weight of the personal cleansingcompositions. Preferred pyridinethione salts are those formed from heavymetals such as zinc, tin, cadmium, magnesium, aluminum and zirconium.Zinc salts are most preferred, especially the zinc salt of1-hydroxy-2-pyridinethione (zinc pyridinethione, ZPT). Other cationssuch as sodium may also be suitable.

Pyridinethione antidandruff agents are well known in the personalcleansing art, and are described, for example, in U.S. Pat. No.2,809,971; U.S. Pat. No. 3,236,733; U.S. Pat. No. 3,753,196; U.S. Pat.No. 3,761,418; U.S. Pat. No. 4,345,080; U.S. Pat. No. 4,323,683; U.S.Pat. No. 4,379,753; and U.S. Pat. No. 4,470,982, which descriptions areincorporated herein by reference.

Sulfur may also be used as the particulate antidandruff agent in thepersonal cleansing compositions herein. Effective concentrations of theparticulate sulfur are generally from about 1% to about 5%, morepreferably from about 2% to about 5%, by weight of the compositions.

Octopirox and related salts and derivatives may also be used as theantidandruff agent in the personal cleansing compositions. Suchantidandruff agents are soluble in the personal cleansing compositionand, therefore, do not disperse throughout the composition ascrystalline particulates as do the other antidandruff agents describedhereinbefore. Other antidandruff agents such as azoles may also be used.Examples of azole antidandruff agents are: ketoconazole, itraconazole,fluconazole, miconazole, econazole.

Water soluble non-particulate antidandruff substances whose depositionand retention is enhanced by the water-soluble nitrogen containingpolymers described herein include (i.e. deposition polymers)

(a) 1-hydroxy-2-pryidoner of the formula

wherein R₁ is hydrogen, alkyl of 1 to 17 carbon atoms, cycloalkyl-alkylof 1 to 4 alkyl carbon atoms, the cycloalkyl groups being optionallysubstituted by alkyl groups of 1 to 4 carbon atoms, aryl, aralkylof 1 to4 alkyl carbon atoms, aryl-alkenyl of 2 to 4 alkenyl carbon atoms,aryloxy-alkyl or arylthio-alkyl of 1 to 4 alkyl carbon atoms, benzhydyl,phenylsulfonyl-alky of 1 to 4 alkyl carbon atoms, furyl or furyl-alkenylof 2 to 4 alkenyl carbon atoms, the aryl groups being optionallysubstituted by alkyl of 1 to 4 carbon atoms, by alkoxyl of 1 to 4 carbonatoms, by nitrogen, or cyano halogen atoms. R₂ is hydrogen, alkyl of 1to 4 carbon atoms, alkenyl or alkinyl of 2 to 4 carbon atoms, halogenatoms or benzyl. R₃ is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.R₄ is hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbonatoms, methoxy-methyl, halogen or benzyl and/or salts thereof.

These compounds are disclosed and more fully described in U.S. Pat. No.4,185,106 and such compounds are available commercially from HoechstAkitengeselfschaft under the trade name Octopirox.

(b) magnesium sulfate adducts of 2,2′-dithiobis(pyridine-1-oxide) of theformula

These compounds are available from Olin corporation under the trade nameOmadine MDS.

It is preferred that an antidandruff agent be used in combination with adeposition polymer, where such a combination would result in improveddeposition and retention of the antidandruff agent.

Additionally, the antidandruff agent can be a heavy metal magnesium oraluminium salts of 1-hydroxy-2-pyridinethione which has the followingstructural formula in tautomeric form, the sulfur being attached to theNo. 2 position in the pyridine ring:

The metal salts represent substitution of the metal cation for thehydrogen of one of the tautomeric forms. Depending, of course, on thevalence of the metal involved there may be more than one of thepyridinethione rings in the compound. Suitable heavy metals includezinc, tin, cadmium and zirconium.

The personal cleansing compositions of the invention can optionallycontain a antidandruff agent which is a platelet pyridinethione saltcrystal. When present, platelet pyridinethione salt crystals arepredominantly flat platelets which have a mean sphericity less thanabout 0.65, preferably between about 0.20 and about 0.65 and a mediansize of at least about 2μ diameter, expressed as the median equivalentdiameter of a sphere of equal volume. It is preferred that the meanparticle size be not greater than 15μ, measured on the same basis. Themedian diameters are on a mass basis with 50% of the mass of particlesfalling on either side of the value given.

The diameter of a sphere of equivalent volume for a particle can bedetermined by a varieties of sedimentation techniques which are based onStokes' Law for the settling velocity of a partivle in a fluid. Suchtechniques are described in Stockham, J. D. and Fochtman, E. G.,Particle Size Analysis, Ann Arbour Science, 1978, incorporated herein byreference.

The sphericity of a particle is also described by Stockham and Fochtmanat page 113 asψ=(d _(v) /d _(s))²where d_(v) is the diameter of a sphere of equivalent volume, supra, andd_(s) is the diameter of a sphere of equivalent area. In the presentinventionthe mean sphericity=(−d _(v) /−d _(s))² orsurface areas of spheres having equivalent volume distribution dividedby the actual surface area of particles as measured. See U.S. Pat. No.4,379,753 to Bolich, Jr incorporated herein by reference.(d) Co-Surfactants

The surfactant system of the personal cleansing compositions used in themethods of the present invention can comprise, one or more detersiveco-surfactants selected from the group consisting of anionicco-surfactant, nonionic co-surfactant, cationic co-surfactant,amphoteric co-surfactant, zwitterionic co-surfactants, and mixturesthereof. The total amount of surfactant present in the personalcleansing composition is preferably at least about 5%, more preferablystill at least about 8%, even more preferably at least about 10%, byweight. Furthermore, the total amount of surfactant (i.e., the mid-chainbranched surfactant plus co-surfactant) present in the personalcleansing composition will be present at preferably less than about 45%,more preferably less than about 35%, even more preferably less thanabout 30%, even more preferably less than about 25%, even morepreferably less than about 20%, most preferably less than about 15%, byweight.

Anionic Co-surfactant—The personal cleansing compositions used in themethods herein preferably comprise an anionic co-surfactant, andpreferably at concentrations of at least about 0.5%, more preferably, atleast about 1%, even more preferably at least about 2%, even morepreferably still at least about 5%, even more preferably still at leastabout 8%, most preferably at least about 10%, by weight. Furthermore,amount of anionic co-surfactant present in the personal cleansingcomposition will be present at preferably less than about 35%, morepreferably less than about 30%, even more preferably less than about25%, by weight of the composition. It is preferred that the total amountof anionic surfactant (i.e. anionic mid-chain branched plus anionicco-surfactant) present in the personal cleansing composition ispreferably about 5% or greater, more preferrably 8% or greater, evenmore preferably about 10% or greater, even more preferably still about12% or greater, by weight of the composition.

Anionic co-surfactants for use in the personal cleansing compositionsinclude alkyl and alkyl ether sulfates. These materials have therespective formulae ROSO₃M and RO(C₂H₄O)_(X)SO₃M, wherein R is alkyl oralkenyl of from about 8 to about 30 carbon atoms, x is 1 to 10, and M isa cation such as ammonium, alkanolamines, such as triethanolamine,monovalent metals, such as sodium and potassium, and polyvalent metalcations, such as magnesium, and calcium. The cation M, of the anionicco-surfactant should be chosen such that the anionic co-surfactantcomponent is water soluble. Solubility will depend upon the particularanionic co-surfactants and cations chosen.

Preferably, R has from about 12 to about 18 carbon atoms in both thealkyl and alkyl ether sulfates. The alkyl ether sulfates are typicallymade as condensation products of ethylene oxide and monohydric alcoholshaving from about 8 to about 24 carbon atoms. The alcohols can bederived from fats, e.g., coconut oil or tallow, or can be synthetic.Lauryl alcohol and straight chain alcohols derived from coconut oil arepreferred herein. Such alcohols are reacted with between about 0 andabout 10, and especially about 3, molar proportions of ethylene oxideand the resulting mixture of molecular species having, for example, anaverage of 3 moles of ethylene oxide per mole of alcohol, is sulfatedand neutralized.

Specific examples of alkyl ether sulfates which may be used in thepersonal cleansing compositions of the present invention are sodium andammonium salts of coconut alkyl triethylene glycol ether sulfate; tallowalkyl triethylene glycol ether sulfate, and tallow alkyl hexaoxyethylenesulfate. Highly preferred alkyl ether sulfates are those comprising amixture of individual compounds, said mixture having an average alkylchain length of from about 10 to about 16 carbon atoms and an averagedegree of ethoxylation of from about 1 to about 4 moles of ethyleneoxide.

Other suitable anionic co-surfactants are the water-soluble salts oforganic, sulfuric acid reaction products of the general formula[R₁—SO₃-M] where R₁ is selected from the group consisting of a straightor branched chain, saturated aliphatic hydrocarbon radical having fromabout 8 to about 24, preferably about 10 to about 18, carbon atoms; andM is a cation, as previously described, subject to the same limitationsregarding polyvalent metal cations as previously discussed. Examples ofsuch co-surfactants are the salts of an organic sulfuric acid reactionproduct of a hydrocarbon of the methane series, including iso-, neo-,and n-paraffins, having about 8 to about 24 carbon atoms, preferablyabout 12 to about 18 carbon atoms and a sulfonating agent, e.g., SO₃,H₂SO₄, obtained according to known sulfonation methods, includingbleaching and hydrolysis. Preferred are alkali metal and ammoniumsulfonated C₁₀₋₁₈ n-paraffins.

Still other suitable anionic co-surfactants are the reaction products offatty acids esterified with isethionic acid and neutralized with sodiumhydroxide where, for example, the fatty acids are derived from coconutoil; sodium or potassium salts of fatty acid amides of methyl tauride inwhich the fatty acids, for example, are derived from coconut oil. Othersimilar anionic co-surfactants are described in U.S. Pat. Nos.2,486,921; 2,486,922; and 2,396,278.

Other anionic co-surfactants suitable for use in the personal cleansingcompositions are the succinnates, examples of which include disodiumN-octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammoniumlauryl sulfosuccinate; tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinnate; diamyl ester ofsodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid;dioctyl esters of sodium sulfosuccinic acid.

Other suitable anionic co-surfactants include olefin sulfonates havingabout 10 to about 24 carbon atoms. The term “olefin sulfonates” is usedherein to mean compounds which can be produced by the sulfonation ofalpha-olefins by means of uncomplexed sulfur trioxide, followed byneutralization of the acid reaction mixture in conditions such that anysulfones which have been formed in the reaction are hydrolyzed to givethe corresponding hydroxy-alkanesulfonates. The sulfur trioxide can beliquid or gaseous, and is usually, but not necessarily, diluted by inertdiluents, for example by liquid SO₂, chlorinated hydrocarbons, etc.,when used in the liquid form, or by air, nitrogen, gaseous SO₂, etc.,when used in the gaseous form.

The alpha-olefins from which the olefin sulfonates are derived aremono-olefins having about 12 to about 24 carbon atoms, preferably about14 to about 16 carbon atoms. Preferably, they are straight chainolefins.

In addition to the true alkene sulfonates and a proportion ofhydroxy-alkanesulfonates, the olefin sulfonates can contain minoramounts of other materials, such as alkene disulfonates depending uponthe reaction conditions, proportion of reactants, the nature of thestarting olefins and impurities in the olefin stock and side reactionsduring the sulfonation process.

A specific alpha-olefin sulfonate mixture of the above type is describedmore fully in the U.S. Pat. No. 3,332,880, which description isincorporated herein by reference.

Another class of anionic co-surfactants suitable for use in the personalcleansing compositions are the beta-alkyloxy alkane sulfonates. Thesecompounds have the following formula:

where R¹ is a straight chain alkyl group having from about 6 to about 20carbon atoms, R² is a lower alkyl group having from about 1 (preferred)to about 3 carbon atoms, and M is a water-soluble cation as hereinbeforedescribed.

Many other anionic co-surfactants suitable for use in the personalcleansing compositions are described in McCutcheon's, Emulsifiers andDetergents, 1989 Annual, published by M. C. Publishing Co., and in U.S.Pat. No. 3,929,678, which descriptions are incorporated herein byreference.

Preferred anionic co-surfactants for use in the personal cleansingcompositions include ammonium lauryl sulfate, ammonium laureth sulfate,triethylamine lauryl sulfate, triethylamine laureth sulfate,triethanolamine lauryl sulfate, triethanolamine laureth sulfate,monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate,diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauricmonoglyceride sodium sulfate, sodium lauryl sulfate, sodium laurethsulfate, potassium lauryl sulfate, potassium laureth sulfate, sodiumlauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoylsarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodiumcocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate,potassium lauryl sulfate, triethanolamine lauryl sulfate,triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate,monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate, andsodium dodecyl benzene sulfonate.

Amphoteric and zwitterionic co-surfactants—The detersive co-surfactantof the personal cleansing compositions used in the methods herein maycomprise an amphoteric and/or zwitterionic co-surfactant. Concentrationsof such co-surfactants will generally range from about 0.5% to about20%, preferably from about 1% to about 10%, by weight of the personalcleansing compositions.

Amphoteric co-surfactants for use in the personal cleansing compositionsinclude the derivatives of aliphatic secondary and tertiary amines inwhich the aliphatic radical is straight or branched and one of thealiphatic substituents contains from about 8 to about 18 carbon atomsand one contains an anionic water solubilizing group, e.g., carboxy,sulfonate, sulfate, phosphate, or phosphonate.

Suitable amphoteric co-surfactants for use in the personal cleansingcompositions include long chain tertiary amine oxides of the formula[R¹R²R³N→O] where R¹ contains an alkyl, alkenyl or monohydroxy alkylradical of from about 8 to about 18 carbon atoms, from 0 to about 10ethylene oxide moieties, and from 0 to about 1 glyceryl moiety, and R²and R³ contain from about 1 to about 3 carbon atoms and from 0 to about1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl, orhydroxypropyl radicals.

Suitable amphoteric co-surfactants for use in the personal cleansingcompositions include long chain tertiary phosphine oxides of the formula[RR′R″P→O] where R contains an alkyl, alkenyl or monohydroxyalkylradical ranging from about 8 to about 18 carbon atoms in chain length,from 0 to about 10 ethylene oxide moieties and from 0 to about 1glyceryl moiety and R′ and R″ are each alkyl or monohydroxyalkyl groupscontaining from about 1 to about 3 carbon atoms.

Suitable amphoteric co-surfactants for use in the personal cleansingcompositions include long chain dialkyl sulfoxides containing one shortchain alkyl or hydroxy alkyl radical of from about 1 to about 3 carbonatoms (usually methyl) and one long hydrophobic chain which includealkyl, alkenyl, hydroxy alkyl, or keto alkyl radicals containing fromabout 8 to about 20 carbon atoms, from 0 to about 10 ethylene oxidemoieties and from 0 to about 1 glyceryl moiety.

Zwitterionic co-surfactants for use in the personal cleansingcompositions include the derivatives of aliphatic quaternary ammonium,phosphonium, and sulfonium compounds, in which the aliphatic radicalsare straight or branched, and wherein one of the aliphatic substituentscontains from about 8 to about 18 carbon atoms and one contains ananionic group, e.g., carboxy, sulfonate, sulfate, phosphate, orphosphonate. A general formula for these compounds is:

where R² contains an alkyl, alkenyl, or hydroxy alkyl radical of fromabout 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxidemoieties and from 0 to about 1 glyceryl moiety; Y is selected from thegroup consisting of nitrogen, phosphorus, and sulfur atoms; R³ is analkyl or monohydroxyalkyl group containing about 1 to about 3 carbonatoms; X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen orphosphorus atom; R⁴ is an alkylene or hydroxyalkylene of from about 1 toabout 4 carbon atoms and Z is a radical selected from the groupconsisting of carboxylate, sulfonate, sulfate, phosphonate, andphosphate groups.

Examples of amphoteric and zwitterionic co-surfactants also includesultaines and amidosultaines. Sultaines and amidosultaines can be usedas foam enhancing co-surfactants that are mild to the eye in partialreplacement of anionic co-surfactants. Sultaines, includingamidosultaines, include for example, cocodimethylpropylsultaine,stearyldimethylpropylsultaine, lauryl-bis-(2-hydroxyethyl)propylsultaine and the like; and the amidosultaines such ascocoamidodimethylpropylsultaine, stearylamidododimethylpropylsultaine,laurylamidobis-(2-hydroxyethyl) propylsultaine, and the like. Preferredare amidohydroxysultaines such as the C₁₂–C₁₈ hydrocarbyl amidopropylhydroxysultaines, especially C₁₂–C₁₄ hydrocarbyl amido propylhydroxysultaines, e.g., laurylamidopropyl hydroxysultaine andcocamidopropyl hydroxysultaine. Other sultaines are described in U.S.Pat. No. 3,950,417, which descriptions are incorporated herein byreference.

Other suitable amphoteric co-surfactants are the aminoalkanoates of theformula R—NH(CH₂)_(n)COOM, the iminodialkanoates of the formulaR—N[(CH₂)_(m)COOM]₂

and mixtures thereof; wherein n and m are numbers from 1 to 4, R isC₈–C₂₂ alkyl or alkenyl, and M is hydrogen, alkali metal, alkaline earthmetal, ammonium or alkanolammonium.

Examples of suitable aminoalkanoates include n-alkylamino-propionatesand n-alkyliminodipropionates, specific examples of which includeN-lauryl-beta-amino propionic acid or salts thereof, andN-lauryl-beta-imino-dipropionic acid or salts thereof, and mixturesthereof.

Other suitable amphoteric co-surfactants include those represented bythe formula:

wherein R¹ is C₈–C₂₂ alkyl or alkenyl, preferably C₁₂–C₁₆, R² ishydrogen or CH₂CO₂M, R³ is CH₂CH₂OH or CH₂CH₂OCH₂CH₂COOM, R⁴ ishydrogen, CH₂CH₂OH, or CH₂CH₂OCH₂CH₂COOM, Z is CO₂M or CH₂CO₂M, n is 2or 3, preferably 2, M is hydrogen or a cation, such as alkali metal(e.g., lithium, sodium, potassium), alkaline earth metal (beryllium,magnesium, calcium, strontium, barium), or ammonium. This type ofco-surfactant is sometimes classified as an imidazoline-type amphotericco-surfactant, although it should be recognized that it does notnecessarily have to be derived, directly or indirectly, through animidazoline intermediate.

Suitable materials of this type are marketed under the trade nameMIRANOL and are understood to comprise a complex mixture of species, andcan exist in protonated and non-protonated species depending upon pHwith respect to species that can have a hydrogen at R². All suchvariations and species are meant to be encompassed by the above formula.

Examples of co-surfactants of the above formula are monocarboxylates anddicarboxylates. Examples of these materials includecocoamphocarboxypropionate, cocoamphocarboxypropionic acid,cocoamphocarboxyglycinate (alternately referred to ascocoamphodiacetate), and cocoamphoacetate.

Commercial amphoteric co-surfactants include those sold under the tradenames MIRANOL C2M CONC. N.P., MIRANOL C2M CONC. O.P., MIRANOL C2M SF,MIRANOL CM SPECIAL (Miranol, Inc.); ALKATERIC 2CIB (Alkaril Chemicals);AMPHOTERGE W-2 (Lonza, Inc.); MONATERIC CDX-38, MONATERIC CSH-32 (MonaIndustries); REWOTERIC AM-2C (Rewo Chemical Group); and SCHERCOTERICMS-2 (Scher Chemicals).

Betaine co-surfactants (zwitterionic) suitable for use in the personalcleansing compositions are those represented by the formula:

wherein:

-   R₁ is a member selected from the group consisting of    COOM and CH(OH)—CH₂SO₃M-   R₂ is lower alkyl or hydroxyalkyl;-   R₃ is lower alkyl or hydroxyalkyl;-   R₄ is a member selected from the group consisting of hydrogen and    lower alkyl;-   R₅ is higher alkyl or alkenyl;-   Y is lower alkyl, preferably methyl;-   m is an integer from 2 to 7, preferably from 2 to 3;-   n is the integer 1 or 0;-   M is hydrogen or a cation, as previously described, such as an    alkali metal, alkaline earth metal, or ammonium.

The term “lower alkyl” or “hydroxyalkyl” means straight or branchchained, saturated, aliphatic hydrocarbon radicals and substitutedhydrocarbon radicals having from one to about three carbon atoms suchas, for example, methyl, ethyl, propyl, isopropyl, hydroxypropyl,hydroxyethyl, and the like. The term “higher alkyl or alkenyl” meansstraight or branch chained saturated (i.e., “higher alkyl”) andunsaturated (i.e., “higher alkenyl”) aliphatic hydrocarbon radicalshaving from about eight to about 20 carbon atoms such as, for example,lauryl, cetyl, stearyl, oleyl, and the like. It should be understoodthat the term “higher alkyl or alkenyl” includes mixtures of radicalswhich may contain one or more intermediate linkages such as ether orpolyether linkages or non-functional substitutents such as hydroxyl orhalogen radicals wherein the radical remains of hydrophobic character.

Examples of co-surfactant betaines of the above formula wherein n iszero which are useful herein include the alkylbetaines such ascocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine,lauryl dimethyl-alpha-carboxyethylbetaine,cetyldimethylcarboxymethylbetaine,lauryl-bis-(2-hydroxyethyl)carboxymethylbetaine,stearyl-bis-(2-hydroxypropyl)carboxymethylbetaine,oleyldimethyl-gamma-carboxypropylbetaine,lauryl-bis-(2-hydroxypropyl)alpha-carboxyethylbetaine, etc. Thesulfobetaines may be represented by cocodimethylsulfopropylbetaine,stearyldimethylsulfopropylbetaine,lauryl-bis-(2-hydroxyethyl)sulfopropylbetaine, and the like.

Specific examples of amido betaines and amidosulfo betaines useful inthe personal cleansing compositions include the amidocarboxybetaines,such as cocoamidodimethylcarboxymethylbetaine,laurylamidodimethylcarboxymethylbetaine,cetylamidodimethylcarboxymethylbetaine,laurylamido-bis-(2-hydroxyethyl)-carboxymethylbetaine,cocoamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, etc. The amidosulfobetaines may be represented by cocoamidodimethylsulfopropylbetaine,stearylamidodimethylsulfopropylbetaine,laurylamido-bis-(2-hydroxyethyl)-sulfopropylbetaine, and the like.

Nonionic co-surfactant—The personal cleansing compositions used in themethods of the present invention may comprise a nonionic co-surfactantas the detersive co-surfactant component therein. Nonionicco-surfactants include those compounds produced by condensation ofalkylene oxide groups (hydrophilic in nature) with an organichydrophobic compound, which may be aliphatic or alkyl aromatic innature.

Concentrations of such co-surfactants will generally range from about0.01% to about 20%, preferably from about 1% to about 10%, by weight ofthe personal cleansing compositions.

Preferred nonionic co-surfactants for use in the personal cleansingcompositions include the following:

(1) polyethylene oxide condensates of alkyl phenols, e.g., thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to about 20 carbon atoms in either a straight chain orbranched chain configuration, with ethylene oxide, the said ethyleneoxide being present in amounts equal to from about 10 to about 60 molesof ethylene oxide per mole of alkyl phenol;

(2) those derived from the condensation of ethylene oxide with theproduct resulting from the reaction of propylene oxide and ethylenediamine products;

(3) condensation products of aliphatic alcohols having from about 8 toabout 18 carbon atoms, in either straight chain or branched chainconfiguration, with ethylene oxide, e.g., a coconut alcohol ethyleneoxide condensate having from about 10 to about 30 moles of ethyleneoxide per mole of coconut alcohol, the coconut alcohol fraction havingfrom about 10 to about 14 carbon atoms;

(4) alkyl polysaccharide (APS) co-surfactants (e.g. alkylpolyglycosides), examples of which are described in U.S. Pat. No.4,565,647, which description is incorporated herein by reference, andwhich discloses APS co-surfactants having a hydrophobic group with about6 to about 30 carbon atoms and polysaccharide (e.g., polyglycoside) asthe hydrophilic group; optionally, there can be a polyalkylene-oxidegroup joining the hydrophobic and hydrophilic moieties; and the alkylgroup (i.e., the hydrophobic moiety) can be saturated or unsaturated,branched or unbranched, and unsubstituted or substituted (e.g., withhydroxy or cyclic rings); and

(5) polyethylene glycol (PEG) glyceryl fatty esters, such as those ofthe formula R(O)OCH²CH(OH)CH²(OCH²CH²)_(n)OH wherein n is from about 5to about 200, preferably from about 20 to about 100, and R is analiphatic hydrocarbyl having from about 8 to about 20 carbon atoms.

Cationic Co-surfactants—Optional cationic co-surfactants for use asconditioning agents in the methods of the present invention willtypically contain quaternary nitrogen moieties. Examples of suitablecationic co-surfactants are described in following documents, all ofwhich are incorporated by reference herein in their entirety: M.C.Publishing Co., McCutcheon's, Detergents & Emulsifiers, (North Americanedition 1979); Schwartz, et al., Surface Active Agents, Their Chemistryand Technology, New York: Interscience Publishers, 1949; U.S. Pat. No.3,155,591; U.S. Pat. No. 3,929,678; U.S. Pat. No. 3,959,461 and U.S.Pat. No. 4,387,090.

Concentrations of such co-surfactants will generally range from about0.01% to about 20%, preferably from about 1% to about 10%, by weight ofthe personal cleansing compositions.

Examples of suitable cationic co-surfactants are those corresponding tothe general formula:

wherein R₁, R₂, R₃, and R₄ are independently selected from an aliphaticgroup of from 1 to about 22 carbon atoms or an aromatic, alkoxy,polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl grouphaving up to about 22 carbon atoms; and X is a salt-forming anion suchas those selected from halogen, (e.g. chloride, bromide), acetate,citrate, lactate, glycolate, phosphate nitrate, sulfate, andalkylsulfate radicals. The aliphatic groups can contain, in addition tocarbon and hydrogen atoms, ether linkages, and other groups such asamino groups. The longer chain aliphatic groups, e.g., those of about 12carbons, or higher, can be saturated or unsaturated. Preferred is whenR₁, R₂, R₃, and R₄ are independently selected from C1 to about C22alkyl. Especially preferred are cationic materials containing two longalkyl chains and two short alkyl chains or those containing one longalkyl chain and three short alkyl chains. The long alkyl chains in thecompounds described in the previous sentence have from about 12 to about22 carbon atoms, preferably from about 16 to about 22 carbon atoms, andthe short alkyl chains in the compounds described in the previoussentence have from 1 to about 3 carbon atoms, preferably from 1 to about2 carbon atoms.Form of Personal Cleansing Composition

The personal cleansing compositions used in the methods herein may be ofan conventional form. That is, they can be liquids, gels, mousses,solids, bars, pastes and the like. The physical form will be selecteddepending upon the desired properties and the intended use of thecomposition.

Aqueous Liquid Carrier

The personal cleansing compositions used in the methods herein mayfurther contain from about 50% to 99.899%, preferably from about 60% toabout 95%, more preferably from about 70% to about 85%, by weight of anaqueous liquid carrier in which the other essential and optionalcompositions components are dissolved, dispersed or suspended.

One essential component of the aqueous liquid carrier is, of course,water. The aqueous liquid carrier, however, may contain other materialswhich are liquid, or which dissolve in the liquid carrier, at roomtemperature and which may also serve some other function besides that ofa simple filler. Such materials can include, for example, hydrotropesand co-solvents.

Hydrotropes—The aqueous liquid carrier may comprise one or morematerials which are hydrotropes. Hydrotropes suitable for use in thecompositions herein include the C₁–C₃ alkyl aryl sulfonates, C₆–C₁₂alkanols, C₁–C₆ carboxylic sulfates and sulfonates, urea, C₁–C₆hydrocarboxylates, C₁–C₄ carboxylates, C₂–C₄ organic diacids andmixtures of these hydrotrope materials.

Suitable C₁–C₃ alkyl aryl sulfonates include sodium, potassium, calciumand ammonium xylene sulfonates; sodium, potassium, calcium and ammoniumtoluene sulfonates; sodium, potassium, calcium and ammonium cumenesulfonates; and sodium, potassium, calcium and ammonium substituted orunsubstituted naphthalene sulfonates and mixtures thereof.

Suitable C₁–C₈ carboxylic sulfate or sulfonate salts are any watersoluble salts or organic compounds comprising 1 to 8 carbon atoms(exclusive of substituent groups), which are substituted with sulfate orsulfonate and have at least one carboxylic group. The substitutedorganic compound may be cyclic, acylic or aromatic, i.e. benzenederivatives. Preferred alkyl compounds have from 1 to 4 carbon atomssubstituted with sulfate or sulfonate and have from 1 to 2 carboxylicgroups. Examples of this type of hydrotrope include sulfosuccinatesalts, sulfophthalic salts, sulfoacetic salts, m-sulfobenzoic acid saltsand diester sulfosuccinates, preferably the sodium or potassium salts asdisclosed in U.S. Pat. No. 3,915,903.

Suitable C₁–C₄ hydrocarboxylates and C₁–C₄ carboxylates for use hereininclude acetates and propionates and citrates. Suitable C₂–C₄ diacidsfor use herein include succinic, glutaric and adipic acids.

Other compounds which deliver hydrotropic effects suitable for useherein as a hydrotrope include C₆–C₁₂ alkanols and urea.

Preferred hydrotropes for use herein are sodium, potassium, calcium andammonium cumene sulfonate; sodium, potassium, calcium and ammoniumxylene sulfonate; sodium, potassium, calcium and ammonium toluenesulfonate and mixtures thereof. Most preferred are sodium cumenesulfonate and sodium xylene sulfonate and mixtures thereof. Thesepreferred hydrotrope materials can be present in the composition to theextent of from about 0.1% to 8% by weight.

Co-Solvents—A variety of water-miscible liquids such as lower alkanols,diols, other polyols, ethers, amines, and the like may be used as partof the aqueous liquid carrier. Particularly preferred are the C₁–C₄alkanols. Such co-solvents can be present in the compositions herein tothe extent of up to about 8%. These co-solvents are different to thesolvents used in combination with styling polymers as the co-solventsdissolved, dispersed or suspended any or all of the components of thepersonal cleansing compositions. Whereas, the solvent is concerned withonly dispersing, and preferably dissolving, the styling polymer.

Optional Components

The personal cleansing compositions used in the methods of the presentinvention may further comprise one or more optional components known foruse in shampoo, conditioning and other personal cleansing compositions,provided that the optional components are physically and chemicallycompatible with the essential component described herein, or do nototherwise unduly impair product stability, aesthetics or performance.Concentrations of such optional components typically range from about0.001% to about 30% by weight of the personal cleansing compositions,when present.

Optional components include anti static agents, dyes, diluents,emollient oils (such as polyisobutylene, mineral oil, petrolatum andisocetyl stearyl stearate), pearlescent aids, foam boosters,pediculocides, pH adjusting agents, perfumes, preservatives, proteins,antioxidants; chelators and sequestrants; and aesthetic components suchas fragrances, colorings, essential oils, skin sensates, astringents,skin soothing agents, skin healing agents and the like, nonlimitingexamples of these aesthetic components include panthenol and derivatives(e.g. ethyl panthenol), pantothenic acid and its derivatives, clove oil,menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch hazeldistillate, allantoin, bisabalol, dipotassium glycyrrhizinate and thelike, sunscreens, thickeners, vitamins and derivatives thereof (e.g.,ascorbic acid, vitamin E, tocopheryl acetate, retinoic acid, retinol,retinoids, and the like), and viscosity adjusting agents. This list ofoptional components is not meant to be exclusive, and other optionalcomponents can be used.

Laundry Bars

The compositions used in the methods of the present invention may alsobe in the form of Laundry bars. That is, the compositions are designedfor use in hand washing of fabrics and is in the form of a bar.

Detergent surfactant—Laundry bars used in the methods of the presentinvention typically comprise 10% to about 60%, preferably about 15% toabout 40% of an anionic surfactant. A preferred anionic surfactant foruse is an alkyl sulfate (AS) having an alkyl chain of from 10 to 20carbon atoms, a branched-chain alkylbenzene sulfonate (ABS) having analkyl chain of from 10 to 22 carbon atoms, a linear-chain alkylbenzenesulfonate (LAS) having an alkyl chain of from 10 to 22 carbon atoms, andmixtures thereof.

The alkyl portion of said ABS or LAS surfactant preferably contains from10 to 16 carbon atoms, more preferably from 10 to 14 carbon atoms. Mostpreferably, the alkylbenzene sulfonate surfactant is LAS.

The alkyl portion of the AS surfactant preferably contains from 10 to 18carbon atoms, more preferably from 12 to 16 carbon atoms. The ASsurfactant can comprise a mixture of a longer-chain AS, such as onehaving 16 to 18 carbons, and a shorter-chain alkyl such as one having11–13 carbons. Preferred AS surfactants include coconut alkyl sulfate,tallow alkylsulfate, and mixtures thereof; most preferably, coconutalkyl sulfate. A preferred anionic surfactant comprises a mixture of ASand alkylbenzene sulfonate. Also preferred are mixtures of AS and LASsurfacants at a ratio of AS:LAS of about 0:100 to 100:0.

The cation for the ABS, LAS and the AS is preferably sodium, althoughother useful cations include triethanolamine, potassium, ammonium,magnesium, and calcium, or mixtures thereof.

Other optional surfactants include zwitterionic, nonionic, amphotericsurfactants alone or in conjuction with anionic surfactants.

Detergent Builder—The laundry bars used in the methods of the presentinvention comprise from about 5% to about 60% by weight detergentbuilder. Preferred laundry bars comprise from about 5% to about 30%builder, more preferably from about 7% to about 20%, by weight of thebar. These detergent builders can be, for example, water-solublealkali-metal salts of phosphates, pyrophosphates, orthophosphates,tripolyphosphates, higher polyphosphates, and mixtures thereof. Apreferred builder is a water-soluble alkali-metal salt oftripolyphosphate, and a mixture of tripolyphosphate and pyrophosphate.The builder can also be a non-phosphate detergent builder. Specificexamples of a non-phosphorous, inorganic detergency builder includewater-soluble inorganic carbonate and bicarbonate salts. The alkalimetal (e.g., sodium and potassium) carbonates, bicarbonates, andsilicates are particularly useful herein. Specific preferred examples ofbuilders include sodium tripolyphosphates (STPP) and sodiumpyrophosphates (TSPP), and mixtures thereof. Other specificallypreferred examples of builders include zeolite and polycarboxylates.

Sodium carbonate is a particularly preferred ingredient in laundry bars,since in addition to its use as a builder, it can also providealkalinity to the laundry bar for improved detergency, and also canserve as a neutralizing agent for acidic components added in the barprocessing. Sodium carbonate is particularly preferred as a neutralizinginorganic salt for an acid precursor of an anionic surfactant used insuch laundry bars, such as the alkyl sulfuric acid and alkyl benzenesulfonic acid.

Co-polymers of acrylic acid and maleic acid are preferred as auxiliarybuilders, since it has been observed that their use in combination withthe fabric softening clay and the clay flocculating agent furtherstabilizes and improves the clay deposition and fabric softeningperformance.

Optional Laundry Bar Componet

Auxiliary Surfactants—The detergent bars used in the methods of thepresent invention can contain up to about 70% by weight of optionalingredients commonly used in detergent products. A typical listing ofthe classes and species optional surfactants, optional builders andother ingredients useful herein appears in U.S. Pat. No. 3,664,961,issued to Norris on May 23, 1972, and EP 550,652, published on Apr. 16,1992, incorporated herein by reference. The following are representativeof such materials, but are not intended to be limiting.

In addition to the auxiliary surfactants mentioned above, a hydrotrope,or mixture of hydrotropes, can be present in the laundry detergent bar.Preferred hydrotropes include the alkali metal, preferably sodium, saltsof tolune sulfonate, xylene sulfonate, cumene sulfonate, sulfosuccinate,and mixtures thereof. Preferably, the hydrotrope, in either the acidform or the salt form, and being substantially anhydrous, is added tothe linear alkyl benzene sulfonic acid prior to its neutralization. Thehydrotrope will preferably be present at from about 0.5% to about 5% ofthe laundry detergent bar.

Fabric Softening Clay—The fabric softening clay is preferably asmectite-type clay. The smectite-type clays can be described asexpandable, three-layer clays; i.e., alumino-silicates and magnesiumsilicates, having an ion exchange capacity of at least about 50 meq/100g. of clay. Preferably the clay particles are of a size that they cannot be perceived tactilely, so as not to have a gritty feel on thetreated fabric of the clothes. The fabric softening clay can be added tothe bar to provide about 1% to about 30% by weight of the bar, morepreferably from about 5% to about 20%, and most preferably about 8% to14%.

While any of the smectite-type clays described herein are useful in thepresent invention, certain clays are preferred. For example, Gelwhite GPis an extremely white form of smectite-type clay and is thereforepreferred when formulating white granular detergent compositions.Volclay BC, which is a smectite-type clay mineral containing at least 3%iron (expressed as Fe₂O₃) in the crystal lattice, and which has a veryhigh ion exchange capacity, is one of the most efficient and effectiveclays for use in the instant compositions from the standpoint of productperformance. On the other hand, certain smectite-type clays aresufficiently contaminated by other silicate minerals that their ionexchange capacities fall below the requisite range; such clays are of nouse in the instant compositions.

Clay Flocculating Agent—It has been found that the use of a clayflocculating agent in a laundry bar containing softening clay providessurprisingly improved softening clay deposition onto the clothes andclothes softening performance, compared to that of laundry barscomprising softening clay alone. The polymeric clay flocculating agentis selected to provide improved deposition of the fabric softening clay.Typically such materials have a high molecular weight, greater thanabout 100,000. Examples of such materials can include long chainpolymers and copolymers derived from monomers such as ethylene oxide,acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinylalcohol, vinyl pyrrolidone, and ethylene imine. Gums, like guar gums,are suitable as well. The preferred clay flocculating agent is apoly(ethylene oxide) polymer.Other Optional Ingredients—A particularly preferred optional componentof the laundry bars used in the methods present invention is a detergentchelant. Such chelants are able to sequester and chelate alkali cations(such as sodium, lithium and potassium), alkali metal earth cations(such as magnesium and calcium), and most preferably, heavy metalcations such as iron, manganese, zinc and aluminum. Preferred cationsinclude sodium, magnesium, zinc, and mixtures thereof. The detergentchelant is particularly beneficial for maintaining good cleaningperformance and improved surfactant mileage, despite the presence of thesoftening clay and the clay flocculating agent.

The detergent chelant is preferably a phosphonate chelant, particularone selected from the group consisting of diethylenetriaminepenta(methylene phosphonic acid), ethylene diamine tetra(methylenephosphonic acid), and mixtures and salts and complexes thereof, and anacetate chelant, particularly one selected from the group consisting ofdiethylenetriamine penta(acetic acid), ethylene diamine tetra(aceticacid), and mixtures and salts and complexes thereof. Particularlypreferred are sodium, zinc, magnesium, and aluminum salts and complexesof diethylenetriamine penta(methylene phosphonate) diethylenetriaminepenta (acetate), and mixtures thereof.

Preferably such salts or complexes have a molar ratio of metal ion tochelant molecule of at least 1:1, preferably at least 2:1.

The detergent chelant can be included in the laundry bar at a level upto about 5%, preferably from about 0.1% to about 3%, more preferablyfrom about 0.2% to about 2%, most preferably from about 0.5% to about1.0%. Such detergent chelant component can be used beneficially toimprove the surfactant mileage of the present laundry bar, meaning thatfor a given level of anionic surfactant and level of detergent chelant,equivalent sudsing and cleaning performance can be achieved compared toa similar bar containing a higher level of the anionic surfactant butwithout the detergent chelant.

Another preferred additional component of the laundry bar is fattyalcohol having an alkyl chain of 8 to 22 carbon atoms, more preferablyfrom 12 to 18 carbon atoms. Fatty alcohol is effective at reducing thebar wear rate and smear (mushiness) of the present laundry bars. Apreferred fatty alcohol has an alkyl chain predominantly containing from16 to 18 carbon atoms, so-called “high-cut fatty alcohol,” which canexhibit less base odor of fatty alcohol relative to broad cut fattyalcohols. Typically fatty alcohol is contained in the laundry bar at upto a level of 10%, more preferably from about 0.75% to about 6%, mostpreferably from about 2% to about 5%. The fatty alcohol is generallyadded to the formulation of the present invention as free fatty alcohol.However, low levels of fatty alcohol can be introduced into the bars asimpurities or as unreacted starting material. For example, laundry barsbased on coconut fatty alkyl sulfate can contain, as unreacted startingmaterial, from 0.1% to 3.5%, more typically from 2% to 3%, by weight offree coconut fatty alcohol on a coconut fatty alkyl sulfate basis.

Another preferred optional component in the laundry bar is a dyetransfer inhibiting (DTI) ingredient to prevent diminishing of colorfidelity and intensity in fabrics. A preferred DTI ingredient caninclude polymeric DTI materials capable of binding fugitives dyes toprevent them from depositing on the fabrics, and decolorization DTImaterials capable of decolorizing the fugitives dye by oxidation. Anexample of a decolorization DTI is hydrogen peroxide or a source ofhydrogen peroxide, such as percarbonate or perborate. Non-limitingexamples of polymeric DTI materials include polyvinylpyrridine N-oxide,polyvinylpyrrolidone (PVP), PVP-polyvinylimidazole copolymer, andmixtures thereof. Copolymers of N-vinylpyrrolidone and N-vinylimidazolepolymers (referred to as “PVPI”) are also preferred for use herein.

Another preferred optional component in the laundry bar is a secondaryfabric softener component in addition to the softening clay. Suchmaterials can be used at levels of about 0.1% to 5%, more preferablyfrom 0.3% to 3%, and can include: amines of the formula R₄R₅R₆N, whereinR₄ is C5 to C₂₂ hydrocarbyl, R₅ and R₆ are independently C₁ to C₁₀hydrocarbyl. One preferred amine is ditallowmethyl amine; complexes ofsuch amines with fatty acid of the formula R₇COOH, wherein R₇ is C₉ toC₂₂ hydrocarbyl, as disclosed in EP No. 0,133,804; complexes of suchamines with phosphate esters of the formula R₈O—P(O)(OH)—OR₉ andHO—P(O)(OH)—OR₉, wherein R₈ and R₉ are independently C₁ to C₂₀ alkyl ofalkyl ethoxylate of the formula -alkyl-(OCH₂CH₂); cyclic amines such asimidazolines of the general formula 1-(higher alkyl) amido (loweralkyl)-2-(higher alkyl)imidazoline, where higher alkyl is from 12 to 22carbons and lower alkyl is from 1 to 4 carbons, such as described in UKPatent Application GB 2,173,827; and quaternary ammonium compounds ofthe formula R₁₀R₁₁R₁₂R₁₃N⁺X⁻, wherein R₁₀ is alkyl having 8 to 20carbons, R₁₁ is alkyl having 1 to 10 carbons, R₁₂ and R₁₃ are alkylhaving 1 to 4 carbons, preferably methyl, and X is an anion, preferablyCl⁻ or Br⁻, such as C₁₂₋₁₃ alkyl trimethyl ammonium chloride.

Yet another optional component in the laundry bar is a bleach component.The bleaching component can be a source of ⁻OOH group, such as sodiumperborate monohydrate, sodium perborate tetrahydrate and sodiumpercarbonate. Sodium percarbonate (2Na₂CO₃.3H₂O₂) is preferred since ithas a dual function of both a source of HOOH and a source of sodiumcarbonate.

Another optional bleaching component is a peracid per se, such as aformula:CH₃(CH₂)_(w)—NH—C(O)—(CH₂)_(z)CO₃Hwherein z is from 2 to 4 and w is from 4 to 10. (The compound of thelatter formula where z is 4 and w is 8 is hereinafter referred to asNAPAA.) The bleaching component can contain, as a bleaching componentstabilizer, a chelating agent of polyaminocarboxylic acids,polyaminocarboxylates such as ethylenediaminotetraacetic acid,diethylenetriaminopentaacetic acid, and ethylenediaminodisuccinic acid,and their salts with water-soluble alkali metals. The bleach componentscan be added to the bar at a level up to 20%, preferably from about 1%to about 10%, more preferably from about 2% to about 6%.

Sodium sulfate is a well-known filler that is compatible with thecompositions of this invention. It can be a by-product of the surfactantsulfation and sulfonation processes, or it can be added separately.

Calcium carbonate (also known as Calcarb) is also a well known and oftenused component of laundry bars. Such materials are typically used atlevels up to 40%, preferably from about 5% to about 25%.

Binding agents for holding the bar together in a cohesive, soluble formcan also be used, and include natural and synthetic starches, gums,thickeners, and mixtures thereof.

Soil suspending agents can be used. In the present invention, their useis balanced with the fabric softening clay/clay flocculating agentcombination to provide optimum cleaning and fabric softeningperformance. Soil suspending agents can also include water-soluble saltsof carboxymethylcellulose and carboxyhydroxymethylcellulose. A preferredsoil suspending agent is an acrylic/maleic copolymer, commerciallyavailable as Sokolan®, from BASF Corp. Other soil suspending agentsinclude polyethylene glycols having a molecular weight of about 400 to10,000, and ethoxylated mono- and polyamines, and quaternary saltsthereof.

Optical brighteners are also preferred optional ingredients in laundrybars of the present invention. Preferred optical brighteners are diaminostilbene, distyrilbiphenyl-type optical brighteners. Preferred asexamples of such brighteners are4,4′-bis{[4-anilino-6-bis(2-hydoxyethyl) amino-1,3,5-trizin-2-yl]amino}stilbene-2,2′-disulfonic acid disodium salt, 4-4′-bis(2-sulfostyryl)biphenyl and 4,4′-bis[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino]stilbene-2,2′-disulfonic acid disodium salt. Such opticalbrighteners, or mixtures thereof, can be used at levels in the bar offrom about 0.05%–1.0%.

Dyes, pigments, germicides, and perfumes can also be added to the barcomposition.

Processing—The detergent laundry bars used in the methods of the presentinvention can be processed in conventional soap or detergent bar makingequipment with some or all of the following key equipment:blender/mixer, mill or refining plodder, two-stage vacuum plodder, logoprinter/cutter, cooling tunnel and wrapper.

In a typical process, the raw materials are mixed in the blender.Alkylbenzene sulfonic acid (when used) is added into a mixture ofalkaline inorganic salts (preferably which includes sodium carbonate)and the resulting partially neutralized mixture is mechanically workedto effect homogeneity and complete neutralization of the mixture. Oncethe neutralization reaction is completed, the alkyl sulfate surfactantis added, followed by the remaining other ingredient materials. Themixing can take from 1 minute to 1 hour, with the usual mixing timebeing from 2 to 20 minutes. The blender mix is discharged to a surgetank. The product is conveyed from the surge tank to the mill orrefining plodder via a multi-worn transfer conveyor.

The alkyl benzene sulfonic acid (HLAS) can be made by well-knownprocesses, such as with SO₃ or oleum. It can be preferably to includeexcess inorganic sulfuric acid (H₂SO₄) in the stock of HLAS, which, uponneutralization, helps to increase the temperature of the product due tothe heat of neutralization of the inorganic sulfuric acid.

After milling or preliminary plodding, the product is then conveyed to adouble stage vacuum plodder, operating at a high vacuum, e.g. 600 to 740millimeters of mercury vacuum, so that entrapped air is removed. Theproduct is extruded and cut to the desired bar length, and printed withthe product brand name. The printed bar can be cooled, for example in acooling tunnel, before it is wrapped, cased, and sent to storage.

Examples of compositions of the present invention are listed hereafterby way of exemplification, and not by way of limitation.

EXAMPLES

The following examples illustrate the preparation and performanceadvantages of the suds boosting polymers containing compositions of theinstant invention. Such examples, however, are not necessarily meant tolimit or otherwise define the scope of the invention herein. All parts,percentages and ratios used herein are expressed as percent weightunless otherwise specified. In the following Examples, the abbreviationsfor the various ingredients used for the compositions have the followingmeanings.

ABBREVIATIONS LAS Sodium linear alkyl benzene sulfonate MLAS ModifiedAlkyl Benzene sulfonate MBAS_(x) Mid-chain branched primary alkyl(average total carbons = x) sulfate MBAE_(x)S_(z) Mid-chain branchedprimary alkyl (average total carbons = z) ethoxylate (average EO = x)sulfate, sodium salt MBAE_(x) Mid-chain branched primary alkyl (averagetotal carbons = x) ethoxylate (average EO = 5) Endolase Endoglunaseenzyme of activity 3000 CEVU/g sold by NOVO Industries A/S MEAMonoethanolamine PG Propanediol BPP Butoxy - propoxy - propanol EtOHEthanol NaOH Solution of sodium hydroxide NaTS Sodium toluene sulfonateCitric acid Anhydrous citric acid CxyFA C_(1x)–C_(1y) fatty acid CxyEz AC_(1x–1y) branched primary alcohol condensed with an average of z molesof ethylene oxide Carbonate Anhydrous sodium carbonate with a particlesize between 200 μm and 900 μm Citrate Tri-sodium citrate dihydrate ofactivity 86.4% with a particle size distribution between 425 μm and 850μm TFAA C16–18 alkyl N-methyl glucamide LMFAA C12–14 alkyl N-methylglucamide APA C8–C10 amido propyl dimethyl amine Fatty Acid C12–C14fatty acid (C12/14) Fatty Acid Topped palm kernel fatty acid (TPK) FattyAcid Rapeseed fatty acid (RPS) Borax Na tetraborate decahydrate PAAPolyacrylic Acid (mw = 4500) PEG Polyethylene glycol (mw = 4600) MESAlkyl methyl ester sulfonate SAS Secondary alkyl sulfate NaPS Sodiumparaffin sulfonate C45AS Sodium C₁₄–C₁₅ linear alkyl sulfate CxyASSodium C_(1x)–C_(1y) alkyl sulfate (or other salt if specified) CxyEzSSodium C_(1x)–C_(1y) alkyl sulfate condensed with z moles of ethyleneoxide (or other salt if specified) CxyEz A C_(1x–1y) branched primaryalcohol condensed with an average of z moles of ethylene oxide AQAR₂.N⁺(CH₃)_(x)((C₂H₄O)yH)z with R₂ = C₈–C₁₈ x + z = 3, x = 0 to 3, z = 0to 3, y = 1 to 15. STPP Anhydrous sodium tripolyphosphate Zeolite AHydrated Sodium Aluminosilicate of formula Na₁₂(Al0₂SiO₂)₁₂.27H₂O havinga primary particle size in the range from 0.1 to 10 micrometers NaSKS-6Crystalline layered silicate of formula δ —Na₂Si₂O₅ Carbonate Anhydroussodium carbonate with a particle size between 200 μm and 900 μmBicarbonate Anhydrous sodium bicarbonate with a particle sizedistribution between 400 μm and 1200 μm Silicate Amorphous SodiumSilicate (SiO₂:Na₂O; 2.0 ratio) Sulfate Anhydrous sodium sulfate PAEethoxylated (15–18) tetraethylene pentamine PIE ethoxylated polyethyleneimine PAEC methyl quatemized ethoxylated dihexylene triamine MA/AACopolymer of 1:4 maleic/acrylic acid, average molecular weight about70,000. CMC Sodium carboxymethyl cellulose Protease Proteolytic enzymeof activity 4 KNPU/g sold by NOVO Industries A/S under the tradenameSavinase Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold byNOVO Industries A/S under the tradename Carezyme Amylase Amylolyticenzyme of activity 60 KNU/g sold by NOVO Industries A/S under thetradename Termamyl 60T Lipase Lipolytic enzyme of activity 100 kLU/gsold by NOVO Industries A/S under the tradename Lipolase PB1 Anhydroussodium perborate bleach of nominal formula NaBO₂.H₂O₂ PercarbonateSodium Percarbonate of nominal formula 2Na₂CO₃.3H₂O₂ NaDCC Sodiumdichloroisocyanurate NOBS Nonanoyloxybenzene sulfonate, sodium salt TAEDTetraacetylethylenediamine DTPMP Diethylene triamine penta (methylenephosphonate), marketed by Monsanto under Trade name Dequest 2060Photoactivated bleach Sulfonated Zinc Phthalocyanine bleach encapsulatedin dextrin soluble polymer Brightener 1 Disodium4,4′-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium4,4′-bis(4-anilino-6-morpholino-1.3.5-triazin-2- yl)amino)stilbene-2:2′-disulfonate. HEDP 1,1-hydroxyethane diphosphonic acid SRP1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephthaloylbackbone SRP 2 sulfonated ethoxylated terephthalate polymer SRP 3 methylcapped ethoxylated terephthalate polymer Silicone Polydimethylsiloxanefoam controller with siloxane- antifoam oxyalkylene copolymer asdispersing agent with a ratio of said foam controller to said dispersingagent of 10:1 to 100:1. SUDS1 Poly(DMAM-co-DMA) (3:1) Copolymer preparedaccording to Example 1 below SUDS2 (DMAM), prepared according to Example2 below SUDS3 Poly(DMAM-co-AA) (2:1) Copolymer prepared according toExample 3 below SUDS4 Poly(DMAM-co-MAA) (2:1) Copolymer preparedaccording to Example 4 below SUDS5 Poly(DMAM-co-MAA-co-AA) (4:1:1)Terpolymer prepared according to Example 5 below SUDS6Poly(DMAM-co-MAA-co-DMA) (4:1:1) Terpolymer prepared according toExample 6 below SUDS7 (DMAM), prepared according to Example 7 belowSUDS8 Poly(DMA-co-DMAM) (3:1) Copolymer, prepared according to Example 8below SUDS9 zwitterionic polymer prepared according to Example 9 belowSUDS10 zwitterionic polymer prepared according to Example 10 belowSUDS11 Polypeptide comprising Lys, Ala, Glu, Tyr (5:6:2:1) having amolecular weight of approximately 52,000 daltons SUDS12 Lysozyme SUDS13LX1279 available from Baker Petrolite Isofol 16 Condea trademark for C16(average) Guerbet alcohols CaCl2 Calcium chloride MgCl2 Magnesiumchloride DTPA Diethylene triamine pentaacetic acid

Example 1

Preparation of Poly(DMAM-co-DMA) (3:1) Copolymer

2-(Dimethylamino)ethyl methacrylate (20.00 g, 127.2 mmol),N,N-dimethylacrylamide (4.20 g 42.4 mmol), 2,2′-azobisisobutyronitrile(0.14 g, 0.85 mmol), 1,4-dioxane (75 ml) and 2-propanol (15 ml) areplaced into a 250 ml three-necked round-bottomed flask, fitted with aheating mantle, magnetic stirrer, internal thermometer and argon inlet.The mixture is subjected to three freeze-pump-thaw cycles to removedissolved oxygen. The mixture is heated for 18 hours with stirring at65° C. TLC (diethyl ether) indicates consumption of monomer. The mixtureis concentrated under vacuum by rotary evaporation to remove thesolvent. Water is added to make a 10% solution and the mixture isdialyzed (3500 MWCO) against water, lyophilized and then pulverized in ablender to yield a white powder. NMR is consistent with the desiredcompound.

Example 2

Preparation of Poly(DMAM) Polymer

2-(Dimethylamino)ethyl methacrylate (3000.00 g, 19.082 mol),2,2′-azobisisobutyronitrile (15.67 g, 0.095 mol), 1,4-dioxane (10.5 L)and 2-propanol (2.1 L) are placed into a 22 L three-neckedround-bottomed flask, fitted with a reflux condenser, heating mantle,mechanical stirrer, internal thermometer and argon inlet. The mixture issparged with argon for 45 minutes with vigorous stirring to removedissolved oxygen. The mixture is heated for 18 hours with stirring at65° C. TLC (diethyl ether) indicates consumption of monomer. The mixtureis concentrated under vacuum by rotary evaporation to remove the bulk ofsolvent. A 50:50 mixture of water:t-butanol is added to dissolve theproduct and the t-butanol is removed under vacuum by rotary evaporation.Water is added to make a 10% solution and the mixture is lyophilized andthen pulverized in a blender to yield a white powder. NMR is consistentwith the desired compound.

Example 3

Preparation of Poly(DMAM-co-AA) (2:1) Copolymer

2-(Dimethylamino)ethyl methacrylate (90.00 g, 572.4 mmol), acrylic acid(20.63 g, 286.2 mmol), 2,2′-azobisisobutyronitrile (0.70 g, 4.3 mmol),1,4-dioxane (345 ml) and 2-propanol (86 ml) are placed into a 1000 mlthree-necked round-bottomed flask, fitted with a heating mantle,magnetic stirrer, internal thermometer and argon inlet. The mixture issparged with nitrogen for 30 minutes to remove dissolved oxygen. Themixture is heated for 18 hours with stirring at 65° C. TLC (diethylether) indicates consumption of monomer. The mixture is concentratedunder vacuum by rotary evaporation to remove the solvent. Water is addedto make a 10% solution and the mixture is lyophilized and thenpulverized in a blender to yield an off-white-peach powder. NMR isconsistent with the desired compound.

Example 4

Preparation of Poly(DMAM-co-MAA) (2:1) Copolymer

2-(methylamino)ethyl methacrylate (98.00 g, 623.3 mmol), methacrylicacid (26.83 g, 311.7 mmol), 2,2′-azobisisobutyronitrile (0.77 g, 4.7mmol), 1,4-dioxane (435 ml) and 2-propanol (108 ml) are placed into a1000 ml three-necked round-bottomed flask, fitted with a heating mantle,magnetic stirrer, internal thermometer and argon inlet. The mixture issparged with nitrogen for 30 minutes to remove dissolved oxygen. Themixture is heated for 18 hours with stirring at 65° C. TLC (diethylether) indicates consumption of monomer. The mixture is concentratedunder vacuum by rotary evaporation to remove the solvent. Water is addedto make a 10% solution and the mixture is lyophilized and thenpulverized in a blender to yield a white powder. NMR is consistent withthe desired compound.

Example 5

Poly(DMAM-co-MAA-co-AA) (4:1:1) Terpolymer

Poly(DMAM-co-MAA-co-AA) (4:1:1). The procedure of Example 4 is repeatedwith the substitution of an equimolar amount of methacrylic acid with a1:1 mixture of methacrylic acid and acrylic acid.

Example 6

Poly(DMAM-co-MAA-co-DMA) (4:1:1) Terpolymer

Poly(DMAM-co-MAA-co-AA) (4:1:1). The procedure of Example 4 is repeatedwith the substitution of an equimolar amount of methacrylic acid with a1:1 mixture of methacrylic acid and N,N-dimethylacrylamide.

Example 7

Preparation of Poly(DMAM) Polymer

Polyacrylic acid is esterified with 2-(dimethylamino)ethanol using wellknown methods such as one described in Org. Syn. Coll. Vol. 3 610(1955).

Example 8

Preparation of Poly(DMA-co-DMAM) (3:1) Copolymer

The procedure of Example 1 is repeated except that2-(dimethylamino)ethyl methacrylate (6.67 g, 42.4 mmol),N,N-dimethylacrylamide (12.6 g 127.2 mmol) is used instead, to give aratio in the polymer of DMA to DMAM of 3:1.

Example 9 Preparation of Zwitterionic Polymer

Reaction of (1-octene/maleic Anhydride) Copolymer with 1 Equivalent ofDMAPA

Poly(maleic anhydride-alt-1-octene) (15.00 g) and tetrahydrofuran (200ml, anhydrous) are placed into a 250 ml three-necked round-bottom flask,fitted with a heating mantle, magnetic stirrer, dropping funnel,internal thermometer and argon inlet. 3-Dimethylaminopropylamine (7.65g, 74.87 mmol) is added dropwise over 15 minutes, with an exotherm to30° C. and heavy precipitation. The mixture is stirred for 4 hours at55° C. The mixture is poured into 3:1 ethyl ether:hexanes to precipitatethe product which is dried under vacuum to yield a white powder. NMR isconsistent with the desired compound.

Example 10

Reaction of (1-hexene/maleic Anhydride) Copolymer with 1 Equivalent ofDMAPA

Poly(maleic anhydride-alt-1-hexene) (15.00 g) and pyridine (150 ml,anhydrous) are placed into a 250 ml three-necked round-bottom flask,fitted with a heating mantle, magnetic stirrer, dropping funnel,internal thermometer and argon inlet. There is a slight exotherm and themixture is dark. 3-Dimethylaminopropylamine (9.25 g, 90.53 mmol) isadded dropwise over 15 minutes, with an exotherm to 45° C. The mixtureis stirred for 4 hours at 80° C. The mixture is concentrated by rotaryevaporation, dissolved into water and lyophilized to yield a yellowpowder. NMR is consistent with the desired compound.

Example 11 Preparation of LAS Powder for Use as a Structurant

Sodium C₁₂ linear alkyl benzene sulfonate (NaLAS) is processed into apowder containing two phases. One of these phases is soluble in thenon-aqueous liquid detergent compositions herein and the other phase isinsoluble. It is the insoluble fraction which serves to add structureand particle suspending capability to the non-aqueous phase of thecompositions herein.

NaLAS powder is produced by taking a slurry of NaLAS in water(approximately 40–50% active) combined with dissolved sodium sulfate(3–15%) and hydrotrope, sodium sulfosuccinate (1–3%). The hydrotrope andsulfate are used to improve the characteristics of the dry powder. Adrum dryer is used to dry the slurry into a flake. When the NaLAS isdried with the sodium sulfate, two distinct phases are created withinthe flake. The insoluble phase creates a network structure of aggregatesmall particles (0.4–2 um) which allows the finished non-aqueousdetergent product to stably suspend solids.

The NaLAS powder prepared according to this example has the followingmakeup shown below.

LAS Powder Component Wt. % NaLAS 85% Sulfate 11% Sulfosuccinate  2%Water 2.5%  Unreacted, etc. balance to 100% % insoluble LAS 17% # ofphase (via X-ray diffraction) 2

Example 12

Non-aqueous based heavy duty liquid laundry detergent compositions (A toE) which comprise the mid-chain branched surfactants of the presentinvention are presented below.

Non-Aqueous Liquid Detergent Composition with Bleach Component Wt % A Wt% B Wt % C Wt % D Wt % E LAS, From Example I 16 13 36 8 2 Mid-branchedSurfactant 22 25 0 30 34 BPP 19 19 19 19 19 Sodium citrate dihydrate 3 33 3 3 Bleach activator 5.9 5.9 5.9 5.9 5.9 Sodium carbonate 9 9 9 9 9SUDS3 0.2 0.5 1.0 0.1 0.5 Maleic-acrylic copolymer 3 3 3 3 3 Coloredspeckles 0.4 0.4 0.4 0.4 0.4 EDDS 1 1 1 1 1 Cellulase Prills 0.1 0.1 0.10.1 0.1 Amylase Prills 0.4 0.4 0.4 0.4 0.4 Ethoxylated diamine quat 1.31.3 1.3 1.3 1.3 Sodium Perborate 15 15 15 15 15 Optionals including:balance balance balance balance balance brightener, colorant, perfume,thickener, suds suppressor, colored speckles etc. 100% 100% 100% 100%100%

The resulting compositions are stable, anhydrous heavy-duty liquidlaundry detergents which provide excellent stain and soil removalperformance when used in normal fabric laundering operations.

Example 13

A non-limiting example of bleach-containing nonaqueous liquid laundrydetergent is prepared having the composition as set forth below.

Component Wt. % Range (% wt.) Liquid Phase LAS 25.0 18–35 C₂₄ E5 orMBAE_(14.3) 13.6 10–20 Hexylene glycol 27.3 20–30 Perfume 0.4   0–1.0SUDS1 0.2 0.01 to 5.0 MBAE₂S_(14.4) 2.3   1–3.0 Solid Phase Protease 0.4  0–1.0 Citrate 4.3 3–6 PB1 3.4 2–7 NOBS 8.0  2–12 Carbonate 13.9  5–20DTPA 0.9   0–1.5 Brightener 1 0.4   0–0.6 Silicone antifoam 0.1   0–0.3Minors Balance —

The resulting composition is an anhydrous heavy duty liquid laundrydetergent which provides excellent stain and soil removal performancewhen used in normal fabric laundering operations.

Example 14

Liquid detergent compositions are made according to the following.

A B C D C₂₅ AE3S 2 8 17 5 MBAS_(14.4) 15 12 0 8 C₁₂–C₁₄ alkyldimethylamine oxide — — — 2 SUDS2 0.1 0.2 2.0 0.7 C₂₅ AS 6 4 6 8 C₂₄ N-methylglucamide 5 4 3 3 C₂₄ AE5 6 1 1 1 C₁₂–C₁₈ fatty acid 11 4 4 3 Citricacid 1 3 3 2 DTPMP 1 1 1 0.5 MEA 8 5 5 2 NaOH 1 2.5 1 1.5 PG 14.5 13.110.0 8 EtOH 1.8 4.7 5.4 1 Amylase (300 KNU/g) 0.1 0.1 0.1 0.1 LipaseD96/L (100 KNU/g) 0.15 0.15 0.15 0.15 Protease (35 g/l) 0.5 0.5 0.5 0.5)Endolase 0.05 0.05 0.05 0.05 Cellulase 0.09 0.09 0.09 0.09Terephthalate-based polymer 0.5 — 0.3 0.3 Boric acid 2.4 2.8 2.8 2.4Sodium xylene sulfonate — 3 — — 2-butyl-octanol 1 1 1 1 Branchedsilicone 0.3 0.3 0.3 0.3 Water & minors Up to 100%

The above liquid detergent compositions (A–D) are found to be veryefficient in the removal of a wide range of stains and is from fabricsunder various usage conditions.

The Following Examples illustrate aqueous based liquid detergentcompositions according to the present invention.

Example 15

Aqueous based heavy duty liquid laundry detergent compositions F to Jwhich comprise the mid-chain branched surfactants of the presentinvention are presented below.

Ingredient F G H I J MBAE1.8S14.4 10 12 14 16 20 Na C25AE1.8S 10 8 6 4 0C23E9 2 2 2 2 2 LMFAA 5 5 5 5 0 SUDS3 0.01 0.2 1.0 1.5 0.8 Citric acidbuilder 3 3 3 3 5 Fatty acid builder 2 2 2 2 0 PAE 1 1 1.2 1.2 0.5 PG 88 8 8 4.5 EtOH 4 4 4 4 2 Boric acid 3.5 3.5 3.5 3.5 2 Sodium Cumene 3 33 3 0 Sulfonate pH = 8.0 8.0 8.0 8.0 7.0 Enzymes, dyes, water balancebalance balance balance balance 100% 100% 100% 100% 100%

Example 16

The following aqueous liquid laundry detergent compositions K to O areprepared in accord with the invention:

K L M N O MBAE1.8S14.4 0 7–12  12–17   17–22   1–35   and/or MBAS14.4Any combination of: 15–21   10–15   5–10  0–5   0–25   C25 AExS * Na (x= 1.8–2.5) C25 AS (linear to high 2-alkyl) C14–17 NaPS C12–16 SAS C181,4 disulfate LAS C12–16 MES LMFAA 0–3.5 0–3.5 0–3.5 0–3.5 0–8    C23E9or C23E6.5 0–2   0–2   0–2   0–2   0–8    SUDS13 0.15 0.35 0.55 1.75 0.3APA 0.5 0.5 0.5 0.5 0.5–2     Citric Acid 5 5 5 5 0–8    Fatty Acid 2 22 2 0–14   (TPK or C12/14) EtOH 4 4 4 4 0–8    PG 6 6 6 6 0–10   MEA 1 11 1 0–3    NaOH 3 3 3 3 0–7    Na TS 2.3 2.3 2.3 2.3 0–4    Na formate0.1 0.1 0.1 0.1 0–1    Borax 2.5 2.5 2.5 2.5 0–5    Protease 0.9 0.9 0.90.9 0–1.3  Lipase 0.06 0.06 0.06 0.06 0–0.3  Amylase 0.15 0.15 0.15 0.150–0.4  Cellulase 0.05 0.05 0.05 0.05 0–0.2  PAE 0–0.6 0–0.6 0–0.6 0–0.60–2.5  PIE 1.2 1.2 1.2 1.2 0–2.5  PAEC 0–0.4 0–0.4 0–0.4 0–0.4 0–2   SRP 2 0.2 0.2 0.2 0.2 0–0.5  Brightener 1 or 2 0.15 0.15 0.15 0.150–0.5  Silicone antifoam 0.12 0.12 0.12 0.12 0–0.3  Fumed Silica 0.00150.0015 0.0015 0.0015 0–0.003 Perfume 0.3 0.3 0.3 0.3 0–0.6  Dye 0.00130.0013 0.0013 0.0013 0–0.003 Moisture/minors Balance Balance BalanceBalance Balance Product pH 7.7 7.7 7.7 7.7 6–9.5  (10% in DI water)Various bar compositions can be made using the method described above.

Example 17

A B C D E F G H I (weight percent) NaCFAS (C_(12–18)) 15.75 15.75 19.1311.20 22.50 13.50 Na(C_(12–18))LAS 6.75 6.75 3.38 8.80 19.00 15.00 21.00Na₂CO₃ 15.00 5.00 15.00 15.00 10.0 3.00 13.0 8.00 10.0 DTPP¹ 0.70 0.700.70 0.70 0.70 0.70 0.60 0.60 SUDS13 0.5 0.1 SUDS3 0.2 0.25 0.8 0.15 0.2SUDS12 0.2 0.2 SUDS1 0.2 0.2 0.2 0.2 PEO-300M² 0.30 0.30 PEO-600M 0.200.20 Bentonite clay 10.0 10.0 5.0 Sokolan CP-5³ 0.40 0.70 0.40 0.70 0.401.00 0.20 TSPP 5.00 5.00 5.00 5.00 5.00 STPP 5.00 10.00 5.00 10.00 10.0015.00 Zeolite 1.25 1.25 1.25 1.25 1.25 1.25 Sodium laurate 9.00 SRP-A⁴0.30 0.30 0.30 0.30 0.30 0.30 0.22 0.22 Protease enzyme⁵ 0.08 0.12 0.080.08 Amylase enzyme⁶ 0.80 0.80 Lipase enzyme 0.10 0.10 Cellulase enzyme⁷0.15 0.15 Balance⁸ ¹Sodium diethylenetriamine penta (phosphonate) ²PEOis poly(ethylene oxide) having a molecular weight as indicated. ³SokolanCP-5 is maleic-acrylic copolymer ⁴SRP-A isNaO₃S(CH₂CH₂O)₂—C(O)—(C₆H₄)—C(O)O—[—CH₂CRH—O—C(O)—(C₆H₄)—C(O)O—]₄—[—CH₂CRH—O—C(O)—(C₆H₄)SO₃Na—C(O)O—]₁—CH₂CH₂OCH₂CH₂SO₃Na,wherein R is H or CH₃ in a ratio of about 1.8:1. ⁵Protease activity at 1Au/gm stock. ⁶Amylase activity at 100,000 amu/gm stock. ⁷Carezyme ®cellulase, supplied by Novo Nordisk, activity at 5000 Cevu/gm stock.⁸Balance comprises water (about 2% to 8%, including water of hydration),sodium sulfate, calcium carbonate, and other minor ingredients.

Example 18

The following compositions were made by mixing the listed ingredients inthe listed proportions. These compositions were used neat to cleanmarble and dilute to clean lacquered wooden floors. Excellent cleaningand surface safety performance was observed.

A B C D E F G H MLAS 3.0 3.0 5.0 3.2 3.2 3.2 8.0 8.0 Dobanol ® 23-3 1.01.0 1.5 1.3 1.3 1.5 3.0 3.5 Empilan KBE21+ 2.0 2.0 2.5 1.9 1.9 2.0 5.06.0 NaPS 2.0 1.5 1.2 1.2 1.0 1.7 3.0 2.5 SUDS5 0.1 2.5 0.1 0.05 0.2 0.30.5 0.25 NaCS 1.2 3.0 2.2 2.0 2.0 1.5 4.0 5.0 MgSO4 0.20 0.9 0.30 0.501.3 2.0 1.0 3.0 Citrate 0.3 1.0 0.5 0.75 1.8 3.0 1.5 6.0 NaHCO3 0.06 0.1— 0.1 — 0.2 — — Na2HPO4 — — 0.1 — 0.3 — — — Na2H2P2O7 — — — — — — 0.20.5 pH 8.0 7.5 7.0 7.25 8.0 7.4 7.5 7.2 Water and Minors q.s. to 100% Asused hereinabove: NaPS stands for Na paraffin sulphonate NaCS stands forNa cumene sulphonate Dobanol ® 23-3 is a C12–13 alcohol ethoxylated withan average ethoxylation degree of 3. Empilan KBE21 is a C12–14 alcoholethoxylated with an average ethoxylation degree of 21.

Example 19

I J K L M N C13–15 EO30 1   — — — — — C12–14 EO20 — — 1   1.7 — — C12–14PO3EO7 — — — — — 2   C12–14 EO10 — — — — 2   — C10–12 EO10 — 1.5 — — — —SUDS7 0.2 0.1 0.3 0.5 0.2 0.1 MLAS — — 2.4 — 2.4 2.4 C11EO5 — — — 5   —— C12–14 EO5 4.2 3.0 3.6 — 3.6 3.6 C9–11 EO4 — 3.0 — — — — C12-OH — 0.3— — — — 2-Hexyl decanol — — — 0.4 — — 2-Butyl octanol 0.3 — 0.3 — 0.30.3 MBAS — — 1.0 — 1.0 1.0 MBAES 1.0 1.3 — 1.5 — — Citrate 0.7 1.0 0.71.0 0.7 0.7 Na2CO3 0.6 0.7 0.6 0.3 0.6 0.6

Example 20

The following compositions were made by mixing the listed ingredients inthe listed proportions:

Weight % Ingredients FF GG HH II MLAS 4 — 3 4 Alcohol ethoxylate 30EO(1) 2 — — 2 Alcohol ethoxylate 12EO (2) — 3 — — Alcohol benzeneethoxylate 10EO (4) — — 3 — SUDS8 0.1 0.2 0.2 0.5 Citric acid 2 2 2 3Butylcarbitol^(R) 4 4 4 7 n-butoxypropoxypropanol — — — 2.5Triethanolamine 1 1 2 1 water & minors q.s. to 100%In the examples hereinabove, (1) is a highly ethoxylated nonionicsurfactant wherein R is a mixture of C₁₃ and C₁₅ alkyl chains and n is30. (2) is a highly ethoxylated nonionic surfactant wherein R is amixture of C₁₃ and C₁₅ alkyl chains and n is 12. (3) is a lowerethoxylated nonionic surfactant wherein n is 7. (4) is a highlyethoxylated nonionic surfactant wherein R is a mixture of C₁₉ and C₂₁alkyl benzene chains and n is 10.Compositions FF-MM described hereinabove can be used neat or diluted. Ina method according to the present invention, these compositions arediluted in 65 times their weight of water and applied to a hard surface.

Example 21

The following compositions were tested for their cleaning performancewhen used diluted on greasy soil.

The following compositions were made by mixing the listed ingredients inthe listed proportions:

Weight % Ingredients NN OO PP Sodium paraffin sulfonate 1.0 3 3 Alcoholethoxylate 7EO 4 — — Alcohol ethoxylate 30EO — 3 2 C12–14 EO21 alcoholethoxylate 1.0 — — SUDS3 0.2 0.3 4.0 MLAS 5.0 0 2 Sodium Citrate 3 3 3Butylcarbitol^(R) 4 4 4 Triethanolamine 1 1 1 water & minors up to 100%

Example 22

A shampoo composition Weight % Components A B TEA C12–C14 Alkyl Sulfate10.00 — NH4 C12–C14 Alkyl (Ethoxy)3 Sulfate — 7.90 SUDS1 0.2 1.0Cocamide MEA 3.00 1.50 Dimethicone DC-200* 3.00 3.00 Ethylene GlycolDisterate 1.50 1.50 Citric acid 0.60 0.60 Trisodium citrate 0.30 — Q.S.Color, preservative, Perfume and q.s. to 100% q.s. to 100% water

Example 23

The following are personal cleansing compositions of the presentinvention.

Weight % Component C D Ammonium Lauryl Sulfate 2.5 9.5 Ammonium Laureth(3) Sulfate 8.5 8.5 JAGUAR C-17¹ 0.5 0.5 MBAS 6.0 — SUDS9 1.0 0.3Coconut Monoethanol Amide 1.0 1.0 Ethylene Glycol Distearate 2.0 2.0Isocetyl Stearoyl Stearate 1.0 1.0 Tricetyl Methyl Ammonium 0.5 0.5Chloride Polydimethylsiloxane² 2.0 2.0 Cetyl Alcohol 0.4 0.4 StearylAlcohol 0.2 0.2 Perfume 1.0 1.0 Color Solution 0.6 0.6 Preservative 0.40.4 Water and Minors q.s to 100% q.s to 100% ¹Tradename for guarhydroxypropyltrimonium chloride, a cationic polymer available fromRhone-Poulenc (Cranbury, NJ, USA). ²A 40/60 weight ratio blend ofpolydimethylsiloxane gum (GE SE 76, available from General Electric Co.,Silicone Products Div., Waterford, NY, USA) and polydimethylsiloxanefluid (about 350 centistokes).The composition can provide excellent in-use hair cleaning andconditioning. As an alternative, the JAGUAR C-17 can be replaced withLUVIQUAT FC 370.

Example 24

The following are personal cleansing compositions of the presentinvention.

Weight % Component E F Ammonium Lauryl Sulfate 4.2 2.2 Ammonium Laureth(3) Sulfate 9.2 9.2 POLYMER LR 400¹ 1.0 1.0 MBAS — 6.0 CoconutMonoethanol Amide 1.0 1.0 Ethylene Glycol Distearate 2.0 2.0 LightMineral Oil 1.0 1.0 Tricetyl Methyl Ammonium 0.5 0.5 Chloride SUDS1 0.751.25 Polydimethylsiloxane² 1.5 1.5 Cetyl Alcohol 0.4 0.4 Stearyl Alcohol0.2 0.2 Perfume 1.2 1.2 Color Solution 0.6 0.6 Preservative 0.4 0.4Water and Minors q.s. to 100% q.s. to 100% ¹Cellulose,2-[2-hydroxy-3-(trimethyl ammonio)propoxy] ethyl ether, chloride, acationic polymer available from Amerchol Corp. (Edison, NJ, USA). ²A40/60 weight ratio blend of polydimethylsiloxane gum (GE SE 76,available from General Electric Co., Silicone Products Div., Waterford,NY, USA) and polydimethylsiloxane fluid (about 350 centistokes).The composition can provide excellent in-use hair cleaning andconditioning

Example 25

The following is an example of a personal cleansing composition of thepresent invention wherein the cationic polymer and anionic surfactantcomponent form a complex coacervate phase.

Weight % Component G Ammonium Laureth (3) Sulfate 4.0 LUVIQUAT FC 370¹0.5 BAS² 13.5 Coconut Monoethanol Amide 1.0 Ethylene Glycol Distearate2.0 Light Mineral Oil 0.5 SUDS8 0.45 Tricetyl Methyl Ammonium Chloride0.5 Polydimethylsiloxane² 3.0 Cetyl Alcohol 0.4 Stearyl Alcohol 0.2Perfume 1.0 Color Solution 0.6 Preservative 0.4 Water and Minors 73.8¹Tradename of BASF Wyandotte Corporation (Parsippany, NJ, USA) forcopolymer of vinyl pyrrolidone and methyl vinyl imidazolium chloride.²The Mid-Chain Branched surfactants according to example II. 3. A 40/60weight ratio blend of polydimethylsiloxane gum (GE SE 76, available fromGeneral Electric Co., Silicone Products Div., Waterford, NY, USA) andpolydimethylsiloxane fluid (about 350 centistokes).The composition can provide excellent in-use hair cleaning andconditioning. As an alternative, the LUVIQUAT FC 370 can be replacedwith JAGUAR C-17.

Example 26

The following is an example of a personal cleansing composition of thepresent invention.

Weight % Component H Cocoamidopropyl Betaine 4.0 Ammonium Laureth (3)Sulfate 8.0 Coconut Monoethanol Amide 2.0 Ethylene Glycol Distearate 2.0Polymer JR-125¹ 1.0 MBAS 4.0 SUDS2 0.2 Isopropyl Isostearate 1.0Tricetyl Methyl Ammonium Chloride 0.5 Polydimethylsiloxane² 1.5 CetylAlcohol 0.4 Stearyl Alcohol 0.2 Perfume 1.0 Color Solution 0.6Preservative 0.4 Water and Minors q.s. to 100% ¹Cellulose,2-[2-hydroxy-3-(trimethyl ammonio)propoxy] ethyl ether, chloride,available from Amerchol Corp. (Edison, NJ, USA). ²VISCASIL 12,500 cSsilicone fluid, available from General Electric (Waterford, NY, USA).

Example 27

The following are personal cleansing compositions of the presentinvention.

Weight % Component I J Ammonium Lauryl Sulfate 8.5 2.0 Ammonium Laureth(3) Sulfate 4.0 4.0 Polymer LM-200¹ 1.0 1.0 MBAS 5.0 11.5 Light MineralOil 1.0 1.0 Coconut Monoethanol Amide 1.0 1.0 Ethylene Glycol Distearate2.0 2.0 SUDS6 0.6 0.1 Tricetyl Methyl Ammonium Chloride 0.5 0.5Polydimethylsiloxane² 3.0 3.0 Cetyl Alcohol 0.4 0.4 Stearyl Alcohol 0.20.2 Perfume 1.0 1.0 Color Solution 0.6 0.6 Preservative 0.4 0.4 Waterand Minors q.s. to q.s. to 100% 100% ¹Polyquaternium 24, a polymericquaternary ammonium salt of hydroxyethyl cellulose reacted with lauryldimethyl ammonium-substituted epoxide, available from Amerchol Corp.(Edison, NJ, USA). ²A 40/60 weight ratio blend of polydimethylsiloxanegum (GE SE 76, available from General Electric Co., Silicone ProductsDiv., Waterford, NY, USA) and polydimethylsiloxane fluid (about 350centistokes).

Example 28

The following is a personal cleansing composition of the presentinvention wherein the cationic polymer and anionic surfactant componentform a complex coacervate phase.

Weight % Component K Ammonium Laureth (3) Sulfate 8.5 GAFQUAT 755N¹ 0.5FLEXAN 130³ 0.5 Coconut Monoethanol Amide 1.0 Ethylene Glycol Distearate2.0 MBAS 8.5 Isocetyl Stearoyl Stearate 1.0 Tricetyl Methyl AmmoniumChloride 0.5 Polydimethylsiloxane² 2.0 Cetyl Alcohol 0.4 SUDS5 0.1Stearyl Alcohol 0.2 Perfume 1.0 Color Solution 0.6 Preservative 0.4Water and Minors q.s. to 100% ¹Copolymer of 1-vinyl-2-pyrrolidone anddimethylamino-ethylmethacrylate, available from GAF Corp., Wayne, NJ,USA. ²VISCASIL, 600,000 cS, from General Electric, Waterford, NY, USA.³Sodium polystyrene sulfonate, an anionic polymer available fromNational Starch and Chemical Corp., Bridgewater, NJ, USA.The composition can provide excellent in-use hair cleaning andconditioning.The example compositions hereof can be made by preparing a premix of theentire amount of silicone conditioning agent to be incorporated into thepersonal cleansing, along with sufficient ammonium sulfate and cetyl andstearyl alcohol such that the premix comprises about 30% siliconeconditioning agent, about 69% surfactant, and about 1% of the alcohols.The premix ingredients are heated and stirred at 72° C. for about 10minutes and the premix is then conventionally mixed with the remaininghot (72° C.) ingredients. The composition is then pumped through a highshear mixer and cooled.

Example 29

The following examples, (L to Z), further describe and demonstrateembodiments within the scope of the present invention. The examples aregiven solely for the purpose of illustration and are not to be construedas limitations of the present invention, as many variations thereof arepossible without departing from the spirit and scope of the invention.These exemplified embodiments of the shampoo compositions of the presentinvention provide cleansing of hair and improved hair conditioningperformance. Ingredients are hereinafter identified by chemical, trade,or CTFA name.

Preparation The shampoo compositions of the present invention can beprepared by using conventional mixing and formulating techniques. Theshampoo compositions illustrated hereinafter in Examples L to Z areprepared in the following manner.

About one-third to all of the total sulfate surfactant (added as a 25%solution) is added to a jacketed mix tank and heated to about 74° C.with slow agitation to form a surfactant solution. Cocamide MEA andfatty alcohol, as applicable, are added to the tank and allowed todisperse. Ethylene glycol distearate (EGDS), as applicable, is thenadded to the mixing vessel, and melted. After the EGDS is well dispersed(usually about 5 to 20 minutes) polyethylene glycol and thepreservative, if used are added and mixed into the surfactant solution.This mixture is passed through a heat exchanger where it is cooled toabout 35° C. and collected in a finishing tank. As a result of thiscooling step, the ethylene glycol distearate crystallizes to form acrystalline network in the product. The remainder of the surfactant andother ingredients including the silicone emulsions are added to thefinishing tank with ample agitation to insure a homogeneous mixture. Asufficient amount of the silicone emulsions are added to provide thedesired level of dimethicone in the final product. Water dispersiblepolymers are typically dispersed in water as a 1% to 10% solution beforeaddition to the final mix. Once all ingredients have been added,ammonium xylene sulfonate or additional sodium chloride can be added tothe mixture to thin or thicken respectively to achieve a desired productviscosity. Preferred viscosities range from about 2500 to about 9000 cSat 25° C. (as measured by a Wells-Brookfield cone and plate viscometerat 15/s).

Component L M N O P Ammonium BAS 2 4 4 5 4 Ammonium BAES 8 6 12 10 12Cocamidopropylbetaine 0 0 2.5 0 1 Jaguar C17⁵ 0.05 0.05 0.05 0.30 0.15SUDS3 0.2 2.5 0.2 0.15 0.5 Cocamide MEA 0.5 0.5 0.80 0.80 0 CetylAlcohol 0 0 0.42 0.42 0.42 Stearyl Alcohol 0 0 0.18 0.18 0.18 EthyleneGlycol Distearate 1.50 1.50 1.50 1.50 1.50 EP Silicone¹ 3.0 2.5 3.0 2.03.0 Perfume Solution 0.70 0.70 0.70 0.70 0.70 DMDM Hydantoin 0.37 0.370.37 0.37 0.37 Color Solution (ppm) 64 64 64 64 64 Water and Minors q.s.to 100% Component Q R S T U Ammonium BAES 9.00 9.00 14.0 14.85 12.50Cocamidopropylbetaine 1.70 1.70 2.70 1.85 4.20 Polyquaternium-10³ 0.050.02 0.15 0.15 0.15 Cocamide MEA 0.80 0.80 0.80 0.80 0 SUDS2 0.2 0.360.42 1.0 0.15 Cetyl Alcohol 0 0 0.42 0.42 0.42 Stearyl Alcohol 0 0 0.180.18 0.18 Ethylene Glycol Distearate 1.50 1.50 1.50 1.50 1.50 EPSilicone⁴ 3.0 2.5 3.0 2.0 3.0 Perfume Solution 0.70 0.70 0.70 0.70 0.70DMDM Hydantoin 0.37 0.37 0.37 0.37 0.37 Color Solution (ppm) 64 64 64 6464 Water and Minors q.s. to 100% Component V W X Y Z Ammonium BAES 14.014.00 14.00 9.00 9.00 Cocamidopropylbetaine 2.70 2.70 2.70 1.70 1.70Polyquaternium-10⁶ 0. 0.15 0.15 0.05 0.02 Cocamide MEA 0.80 0.80 0 0.800.80 Cetyl Alcohol 0 0.42 0 0 0 SUDS9 0.2 0.36 0.58 0.37 1.25 StearylAlcohol 0 0.18 0 0 0 Ethylene Glycol Distearate 0 0 0 1.50 1.50 Carbopol981² 0.50 0.50 0.50 0 0 EP Silicone¹ 3.0 2.5 3.0 2.0 3.0 PerfumeSolution 0.70 0.70 0.70 0.70 0.70 DMDM Hydantoin 0.37 0.37 0.37 0.370.37 Color Solution (ppm) 64 64 64 64 64 Water and Minors q.s. to 100%¹EP Silicone is an experimental emulsion polymerized polydimethylsiloxane of about 97,000 csk with particle size of approximately 300 nmmade via linear feedstock available from Dow Corning (2-1520; 13556-34).²Carbopol 981 is a crosslinked polyacrylate available from B. F.Goodrich. ³Polyquaternium-10 is JR30M, a cationic cellulose derivedpolymer available from Amerchol. ⁴EP Silicone is an experimentalemulsion polymerized polydimethyl siloxane of about 335,000 csk withparticle size of approximately 500 nm made via linear feedstockavailable from Dow Corning (2-1520; PE106004). ⁵Jaguar C17 is a cationicpolymer available from Rhone-Poulenc ⁶Polyquaternium-10 is JR400, acationic cellulose derived polymer available from Amerchol.

Example 30

A shampoo having the following formula is prepared

Component % weight AA BAS 17 Zinc Pyridinethione* 2.0 CoconutMonoethanolamide 3.0 Ethylene Glycol Distereate 5.0 Sodium Citrate 0.5SUDS7 0.3 Citric Acid 0.2 Color solution 0.1 Perfume 0.5 Water q.s. to100.00% BB Triethanolamine alkyl sulfate 10% BAS 9 Zinc Pyridinethione*2.0 Coconut Monoethanolamide 2.0 SUDS1 0.33 Triethanolamine 3.0Magnesium/Aluminium Silicate 0.5 Hydroxy Methyl Cellulose 0.6 Colorsolution 0.1 Perfume 0.3 Water q.s. to 100.00% CC Sodium Alkyl GlycerylSulfonate 5% BAS 15 Zinc Pyridinethione* 2.0 SUDS2 0.2 Sodium Chloride5.0 Sodium N-Lauryl Sarcosinate 12.0 N-Cocoyl Sarcosine Acid 1.0 LauricDiethanolamide 2.0 Color solution 0.12 Perfume 0.5 Water q.s. to 100.00%*The Zinc pyridinethione salt crystals prepared according to the methoddescribed in U.S. Pat. No. 4,379,753 to Bolich.

Example 31

The compositions illustrated in Example 31 (DD to TT), illustratespecific embodiments of the shampoo compositions of the presentinvention, but are not intended to be limiting thereof. Othermodifications can be undertaken by the skilled artisan without departingfrom the spirit and scope of this invention. These exemplifiedembodiments of the shampoo compositions of the present invention provideexcellent cleansing of hair and dandruff control.

All exemplified compositions can be prepared by conventional formulationand mixing techniques. Component amounts are listed as weight percentsand exclude minor materials such as diluents, filler, and so forth. Thelisted formulations, therefore, comprise the listed components and anyminor materials associated with such components.

Component DD EE FF GG HH Ammonium Laureth Sulfate 15.00 15.00 15.0015.00 7.50 BAS 5.00 5.00 5.00 5.00 2.50 Sodium Lauroyl Sarcosinate 1.501.50 1.50 1.50 0.75 Ethylene Glycol Distearate 1.50 1.50 1.50 1.50 1.50SUDS3 0.2 0.55 0.75 0.8 1.25 Zinc Pyrithione 1.00 1.00 1.00 — 1.00Selenium Disulfide — — — 1.00 — Jaguar C17S 0.10 0.05 0.50 0.10 0.10Fragrance q.s. q.s. q.s. q.s. q.s. Color q.s. q.s. q.s. q.s. q.s. pHadjustment (Mono/ q.s. q.s. q.s. q.s. q.s. Disodium Phosphate) viscosityadjustment (Sodium q.s. q.s. q.s. q.s. q.s. Chloride, preservative (DMDMq.s. q.s. q.s. q.s. q.s. Hydantoin); Water Component JJ KK LL MM NN BAES7.50 15.00 15.00 10.00 10.00 BAS 2.50 5.00 5.00 2.50 2.50 CocamidopropylBetaine — — — 2.50 2.50 Sodium Lauroyl Sarcosinate 0.75 — — — — EthyleneGlycol Distearate 1.50 1.50 1.50 1.50 1.50 SUDS6 0.1 0.85 0.15 0.2 0.3Ketoconazole 1.00 1.00 1.00 1.00 1.00 Jaguar C13S — 0.10 — 0.10 — JaguarC17S 0.05 — 0.10 — 0.10 Fragrance q.s. q.s. q.s. q.s. q.s. Color q.s.q.s. q.s. q.s. q.s. pH adjustment (Mono/ q.s. q.s. q.s. q.s. q.s.Disodium Phosphate) Sodium Sulfate, PEG-600, q.s. q.s. q.s. q.s. q.s.Ammonium Xylene Sulfonate) preservative (DMDM q.s. q.s. q.s. q.s. q.s.Hydantoin) Water Component OO PP QQ RR SS TT Ammonium Laureth Sulfate 015.00 0 15.00 15.00 0 BAS 5.00 5.00 5.00 5.00 5.00 5.00 BAES 15.00 015.00 0 0 15.00 Cocamidopropyl Betaine 2.00 — — — — — Sodium LauroylSarcosinate — 1.50 1.50 — — — Sodium Cocoyl Glutamate — — — — — 1.50SUDS5 0.2 0.9 0.1 0.2 0.2 1.5 Ethylene Glycol Distearate 1.50 1.50 1.501.50 1.50 1.50 Stearyl Alcohol — — — — — — Zinc Pyrithione 1.00 0.300.30 0.30 0.30 1.00 Jaguar C13S 0.20 — — 0.10 0.05 — Jaguar C17S — 0.100.05 — — 0.10 Fragrance q.s. q.s. q.s. q.s. q.s. q.s. Color q.s. q.s.q.s. q.s. q.s. q.s. pH adjustment (Mono/ q.s. q.s. q.s. q.s. q.s. q.s.Disodium Phosphate) viscosity adjustment (Sodium q.s. q.s. q.s. q.s.q.s. q.s. Chloride,) preservative (DMDM q.s. q.s. q.s. q.s. q.s. q.s.Hydantoin) Water q.s. q.s. q.s. q.s. q.s. q.s.

In preparing each of the compositions described in Examples DD to TT,about one-third of the surfactant (added as 25 wt % solution) is addedto a jacketed mix tank and heated to about 74° C. with slow agitation toform a surfactant solution. Salts (sodium chloride) and pH modifiers(disodium phosphate, monosodium phosphate) are added to the tank andallowed to disperse. Ethylene glycol distearate (EGDS) is added to themixing vessel and allowed to melt. After the EGDS is melted anddispersed (e.g., after about 5–20 minutes), preservative and additionalviscosity modifier are added to the surfactant solution. The resultingmixture is passed through a heat exchanger where it is cooled to about35° C. and collected in a finishing tank. As a result of this coolingstep, the EGDS crystallizes to form a crystalline network in theproduct. The remainder of the surfactant and other components are addedto the finishing tank with agitation to ensure a homogeneous mixture.Cationic guar polymer is dispersed in water as a 0.5–2.5% aqueoussolution before addition to the final mix. Once all components have beenadded, viscosity and pH modifiers are added to the mixture to adjustproduct viscosity and pH to the extent desired.

Each exemplified composition provides excellent hair cleansing,lathering, antimicrobial agent deposition on the scalp and dandruffcontrol.

Example 32

Component A B C BAES 14.00 14.00 14.00 Cocamidopropyl Betaine — 2.502.50 Cocoamphodiacetate 2.50 — — Cocamide MEA 1.00 1.00 1.00 SUDS12 0.20.2 0.6 Ethylene Glycol Distearate 1.50 1.50 1.50 Cetyl Alcohol 0.420.42 0.42 Stearyl Alcohol 0.18 0.18 0.18 Zinc Pyrithione 1.00 1.00 1.00Jaguar C13S 0.15 0.15 — Jaguar C17S — — 0.15 Fragrance q.s. q.s. q.s.Color q.s. q.s. q.s. pH adjustment (Mono/Di sodium q.s. q.s. q.s.Phosphate) viscosity adjustment (Sodium q.s. q.s. q.s. Chloride,preservative (DMDM Hydantoin); q.s. q.s. q.s. Water

In preparing each of the compositions described in (A to C), from 50% to100% by weight of the detersive surfactants are added to a jacketed mixtank and heated to about 74° C. with slow agitation to form a surfactantsolution. If used, pH modifiers (monosodium phosphate, disodiumphosphate) are added to the tank and allowed to disperse. Ethyleneglycol distearate (EGDS) and fatty alcohols (cetyl alcohol, stearylalcohol) are then added to the mixing vessel and allowed to melt. Afterthe EGDS is melted and dispersed (usually about 5–10 minutes),preservative (if used) is added and mixed into the surfactant solution.Additional viscosity modifier are added to the surfactant solution ifnecessary. The resulting mixture is passed through a heat exchangerwhere it is cooled to about 35° C. and collected in a finishing tank. Asa result of this cooling step, the EGDS crystallizes to form acrystalline network in the product. Any remaining surfactant and othercomponents are added to the finishing tank with agitation to ensure ahomogeneous mixture. Cationic guar polymer is dispersed in water as a0.5–2.5% aqueous solution before addition to the final mix. Once allcomponents have been added, viscosity and pH modifiers are added to themixture to adjust product viscosity and pH to the extent desired.

Each exemplified composition provides excellent hair cleansing,lathering, antimicrobial agent deposition on the scalp, and dandruffcontrol.

Example 33

Weight % Component UU VV WW XX YY BAS 2.0 2.0 3.0 2.0 3.0 Cocamidopropyl6.0 6.0 9.0 6.0 9.0 Betaine FB Alkyl Glyceryl Sulfonate 10.0 10.0 6.010.0 6.0 Mixture A 3.0 6.0 — — — Mixture B — — 3.0 — 6.0 Mixture C — — —3.0 — SUDS3 0.2 0.2 0.3 0.9 0.5 Dihydrogenated Tallowamidoethyl 0.250.50 — 0.25 — Hydroxyethylmonium Methosulfate (1) DitallowamidoethylHydroxypropylmonium — — 0.25 — 0.25 Methosulfate (2) Polyquaternium-16 —— — 0.25 — (Luviquat 905) Monosodium Phosphate 0.1 0.1 0.1 0.1 0.1Disodium Phosphate 0.2 0.2 0.2 0.2 0.2 Glycol Distearate 2.0 2.0 2.0 2.02.0 Cocomonoethanol amide 0.6 0.6 0.6 0.6 0.6 Fragrance 1.0 1.0 1.0 1.01.0 Cetyl Alcohol 0.42 0.42 0.42 0.42 0.60 Stearyl Alcohol 0.18 0.180.18 0.18 — PEG-150 Pentaerythrityl 0.1 0.1 0.1 0.1 0.1 TetrastearatePolyquaternium 10 0.3 — — 0.1 — (JR30M) Polyquaternium 10 — 0.3 — — —(JR400) Polyquaternium 10 — — 0.3 — 0.1 (JR125) Dimethicone — 0.3 0.3 —— DMDM Hydantoin 0.2 0.2 0.2 0.2 0.2 Water qs 100 qs 100 qs 100 qs 100qs 100 (1) Available under the tradename Varisoft 110 from SherexChemical Co. (Dublin, Ohio, USA) (2) Available under the tradenameVarisoft 238 from Sherex Chemical Co. (Dublin, Ohio, USA) Weight %Component ZZ AAA BBB CCC DDD BAES 4.0 5.0 6.0 3.0 4.0 SUDS1 0.2 0.2 0.251.0 2.5 BAS 1.0 1.0 1.0 1.0 1.0 Ammonium Laureth 5.5 4.5 3.5 3.5 4.5Sulfate Sodium 7.5 7.5 7.5 8.5 7.5 Lauroamphoacetate Mixture A 4.0 6.0 —— 4.0 Mixture B — — 4.0 — — Mixture C — — — 4.0 — DihydrogenatedTallowamidoethyl 1.0 — — — — Hydroxyethylmonium Methosulfate (1)Ditallowamidoethyl Hydroxypropylmonium — 0.75 — — — Methosulfate (2)Ditallow Dimethyl — — 1.0 — 1.0 Ammonium Chloride (3) DitallowamidoethylHydroxyethylmonium — — — 0.75 — Methosulfate (4) Polyquaternium-16 — — —0.25 — (Luviquat 905) Monosodium Phosphate 0.1 0.1 0.1 0.1 0.1 DisodiumPhosphate 0.2 0.2 0.2 0.2 0.2 Glycol Distearate 2.0 2.0 2.0 2.0 2.0Cocomonoethanol amide 0.6 0.6 0.6 0.6 0.6 Fragrance 1.0 0.8 1.0 1.0 1.0Cetyl Alcohol 0.42 0.42 0.42 0.42 0.42 Stearyl Alcohol 0.18 0.18 0.180.18 0.18 PEG-150 Pentaerythrityl 0.08 0.1 0.1 0.1 0.1 TetrastearatePolyquaternium 10 0.3 — — 0.1 0.3 (JR30M) Polyquaternium 10 — 0.3 — — —(JR400) Polyquaternium 10 — — 0.3 — — (JR125) Dimethicone — 0.5 0.3 — —DMDM Hydantoin 0.2 0.2 0.2 0.2 0.2 Water qs 100 qs 100 qs 100 qs 100 qs100 (1) Available under the tradename Varisoft 110 from Sherex ChemicalCo. (Dublin, Ohio, USA) (2) Available under the tradename Varisoft 238from Sherex Chemical Co. (Dublin, Ohio, USA) (3) Available under thetradename Adogen 442-110P from Witco (Dublin, Ohio, USA) (4) Availableunder the tradename Varisoft 222 from Sherex Chemical Co. (Dublin, Ohio,USA) Weight % Component EEE FFF GGG HHH III BAES 2.0 3.0 5.0 2.0 3.0 BAS— 1.0 — 1.0 1.0 Ammonium Laureth 0 6.5 4.0 7.0 6.0 SulfateCocamidopropyl 6.0 — 4.7 — — Betaine FB Sodium — 7.5 — 7.5 7.5Lauroamphoacetate SUDS10 0.2 0.2 5.0 0.3 1.2 Alkyl Glyceryl Sulfonate10.0 — — — — Mixture A — — — 4.0 — Mixture C — — — — 4.0 Mixture D 6.04.0 8.0 — — Dihydrogenated Tallowamidoethyl 0.25 — — 0.5 —Hydroxyethylmonium Methosulfate (1) Ditallow Dimethyl — 1.0 — — —Ammonium Chloride (3) Di(partially hardened — — 0.75 — 1.0 soyoylethyl)Hydroxyethylmonium Methosulfate (5) Polyquaternium-16 — — — 0.25 —(Luviquat 905) Monosodium Phosphate 0.1 0.1 0.1 0.1 0.1 DisodiumPhosphate 0.2 0.2 0.2 0.2 0.2 Glycol Distearate 2.0 2.0 2.0 2.0 2.0Cocomonoethanol amide 0.6 0.6 0.6 0.6 0.6 Fragrance 1.0 1.0 1.0 1.0 1.0Cetyl Alcohol 0.42 0.42 0.42 0.42 0.42 Stearyl Alcohol 0.18 0.18 0.180.18 0.18 PEG-150 Pentaerythrityl 0.10 0.08 1.0 0.10 0.08 TetrastearatePolyquaternium 10 — — 0.3 — — (JR30M) Polyquaternium 10 — 0.3 — — —(JR400) Polyquaternium 10 0.3 — — — — (JR125) Guar — — — 0.25 0.5Hydroxypropyltrimonium Chloride Dimethicone — 0.5 — — — DMDM Hydantoin0.2 0.2 0.2 0.2 0.2 Water qs 100 qs 100 qs 100 qs 100 qs 100 (1)Available under the tradename Varisoft 110 from Sherex Chemical Co.(Dublin, Ohio, USA) (3) Available under the tradename Adogen 442-110Pfrom Witco Corpora- tion (Dublin, Ohio, USA) (5) Available under thetradename Armocare EQ-S from Akzo-Nobel Chemicals Inc. (Chicago,Illinois, USA) w/w ratio Mixture A. Styling Polymer: t-butylacrylate/2-ethylhexyl methacrylate 40 (90/10 w/w) Volatile Solvent:isododecane 60 Mixture B. Styling Polymer: t-butyl acrylate/2-ethylhexylmethacrylate 50 (90/10 w/w) Volatile Solvent: isododecane 50 Mixture C.Styling Polymer: t-butyl acrylate/2-ethylhexyl methacrylate/ 40 PDMSmacromer (81/9/10 w/w) Volatile Solvent: isododecane 60 Mixture D.Styling Polymer: vinyl pyrrolidone/vinyl acetate (5/95 w/w) 40 VolatileSolvent: diethyl succinate 60

Example 34

The compositions of the present invention, in general, can be made bymixing together at elevated temperature, e.g., about 72° C. water andsurfactants along with any solids (e.g., amphiphiles) that need to bemelted, to speed mixing into the personal cleansing composition.Additional ingredients including the electrolytes can be added either tothis hot premix or after cooling the premix. The nonionic or anionicpolymers can be added as a water solution after cooling the premix. Theingredients are mixed thoroughly at the elevated temperature and thenpumped through a high shear mill and then through a heat exchanger tocool them to ambient temperature. The silicone may be emulsified at roomtemperature in concentrated surfactant and then added to the cooledproduct. Alternately, for example, the silicone conditioning agent canbe mixed with anionic surfactant and fatty alcohol, such as cetyl andstearyl alcohols, at elevated temperature, to form a premix containingdispersed silicone. The premix can then be added to and mixed with theremaining materials of the personal cleansing composition, pumpedthrough a high shear mill, and cooled.

The personal cleansing compositions illustrated in Example XXII (JJJ toQQQ) illustrate specific embodiments of the personal cleansingcompositions of the present invention, but are not intended to belimiting thereof. Other modifications can be undertaken by the skilledartisan without departing from the spirit and scope of this invention.These exemplified embodiments of the personal cleansing compositions ofthe present invention provide cleansing of hair and/or skin and improvedconditioning.

All exemplified compositions can be prepared by conventional formulationand mixing techniques. Component amounts are listed as weight percentsand exclude minor materials such as diluents, filler, and so forth. Thelisted formulations, therefore, comprise the listed components and anyminor materials associated with such components.

Ingredients JJJ KKK LLL MMM NNN BAES 5.00 — — — — BAS 5.00 7.50 7.507.50 7.50 Sodium alkyl glycerol sulfonate 2.50 2.50 2.50 2.50 2.50Cocoamidopropyl Betaine — — — — — SUDS7 0.2  0.2  0.6  0.5  0.25  GlycolDistearate 2.00 1.50 2.00 2.00 2.00 Cocomonoethanol amide 0.60 0.85 0.850.85 0.85 Cetyl Alcohol 0.42 0.42 0.42 0.42 0.42 Stearyl Alcohol 0.180.18 0.18 0.18 0.18 EDTA (ethylenediamine tetra 0.10 0.10 0.10 0.10 0.10acetic acid) Monosodium phosphate 0.10 0.10 0.10 0.10 0.10 Disodiumphosphate 0.20 0.20 0.20 0.20 0.20 Sodium Benzoate 0.25 0.25 0.25 0.250.25 Hydroxyethylcellulose¹ 0.10 0.25 — — — Hydroxypropyl Guar² — — 0.25— — Hydroxyethylethylcellulose³ — — 0.25 — Polystyrene Sulfonate — — —0.25 Tricetyl methylammonium chloride 0.58 — — — — Perfume 0.60 0.600.60 0.60 0.60 Dimethicone 1.00 1.50 1.50 1.50 1.50 Glydant 0.20 0.200.20 0.20 0.20 NaCl 0.20 0.30 0.30 1.00 0.30 Water and minors q.s. to100% Ingredients OOO PPP QQQ BAES — 9.00 8.00 BAS 6.00 — — Sodium alkylglycerol sulfonate 1.00 2.50 — SUDS8 0.2  0.2  0.2  CocoamidopropylBetaine — 2.50 — Glycol Distearate 1.50 1.50 2.00 Cocomonoethanol amide0.85 0.85 — Cetyl Alcohol 0.42 0.42 0.40 Stearyl Alcohol 0.18 0.18 0.18EDTA (ethylenediamine tetra acetic 0.10 0.10 0.10 acid) Monosodiumphosphate 0.10 0.10 0.10 Disodium phosphate 0.20 0.20 0.20 SodiumBenzoate 0.25 0.25 0.25 Hydroxyethylcellulose¹ 0.25 0.25 0.25Hydroxypropyl Guar² — — — Hydroxyethylethylcellulose³ — — — PolystyreneSulfonate — — — Tricetyl methylammonium chloride — — — Perfume 0.60 0.600.60 Dimethicone 1.50 1.50 — Glydant 0.20 0.20 0.20 SodiumLauroamphoacetate — — 3.60 Polyquaternium-10 — — 0.20 NaCl 0.30 0.30 —Water and minors q.s. to 100% ¹Natrosol 250 HHR from Aqualon ²Jaguar HP60 from Rhone-Poulenc ³Bermocoll E411 FQ from Akzo Nobel

The following are non-limiting examples of liquid detergent compositionscomprising the polymeric suds extenders according to the presentinvention.

Example 35

TABLE I weight % Ingredients A B C C₁₂–C₁₅ Alkyl sulphate — 28.0 25.0C₁₂–C₁₃ Alkyl (E_(0.6–3)) sulfate 30 — — C₁₂ Amine oxide 5.0 3.0 7.0C₁₂–C₁₄ Betaine 3.0 — 1.0 C₁₂–C₁₄ Polyhydroxy fatty acid amide — 1.5 —C₁₀ Alcohol Ethoxylate E₉ ¹ 2.0 — 4.0 Diamine² 1.0 — 7.0 Mg²⁺ (as MgCl₂)0.25 — — Citrate (cit2K3) 0.25 — — Polymeric suds booster³ 1.25 2.6 0.9Minors and water⁴ balance balance balance pH of a 10% aqueous solution 910 10 ¹E₉ Ethoxylated Alcohols as sold by the Shell Oil Co.²1,3-diaminopentane sold as Dytek EP. ³Polypeptide comprising Lys, Ala,Glu, Tyr (5:6:2:1) having a molecular weight of approximately 52,000daltons. ⁴Includes perfumes, dyes, ethanol, etc.

Example 36

TABLE II weight % Ingredients A B C C₁₂–C₁₃ Alkyl (E_(0.6–3)) sulfate —15.0 10.0 Paraffin sulfonate 20.0 — — Na C₁₂–C₁₃ linear alkylbenzenesulfonate 5.0 15.0 12.0 C₁₂–C₁₄ Betaine 3.0 1.0 — C₁₂–C₁₄ Polyhydroxyfatty acid amide 3.0 — 1.0 C₁₀ Alcohol Ethoxylate E₉ ¹ — — 20.0 Diamine²1.0 — 7.0 DTPA³ — 0.2 — Mg²⁺ (as MgCl₂) 1.0 — — Ca²⁺ (as Ca(citrate)₂) —0.5 — Protease⁴ 0.01 — 0.05 Amylase⁵ — 0.05 0.05 Hydrotrope⁶ 2.0 1.5 3.0Polymeric suds booster⁷ 0.5 3.0 0.5 Minors and water⁸ balance balancebalance pH of a 10% aqueous solution 9.3 8.5 11 ¹E₉ Ethoxylated Alcoholsas sold by the Shell Oil Co. ²1,3-bis(methylamino)cyclohexane.³Diethylenetriaminepentaacetate. ⁴Suitable protease enzymes includeSavinase ®; Maxatase ®; Maxacal ®; Maxapem 15 ®; subtilisin BPN andBPN′; Protease B; Protease A; Protease D; Primase ®; Durazym ®;Opticlean ®; and Optimase ®; and Alcalase ®. ⁵Suitable amylase enzymesinclude Termamyl ®, Fungamyl ®; Duramyl ®; BAN ®, and the amylases asdescribed in WO95/26397 and in co-pending application by Novo NordiskPCT/DK/96/00056. ⁶Suitable hydrotropes include sodium, potassium,ammonium or water-soluble substituted ammonium salts of toluene sulfonicacid, naphthalene sulfonic acid, cumene sulfonic acid, xylene sulfonicacid. ⁷Poly(DMAM-co-AA) (2:1) Copolymer of Example 3 ⁸Includes perfumes,dyes, ethanol, etc.

Example 37

TABLE III weight % Ingredients A B C D C₁₂–C₁₅ Alkyl (E₁) sulfate — 30.0— — C₁₂–C₁₅ Alkyl (E_(1.4)) sulfate 30.0 — 27.0 — C₁₂–C₁₅ Alkyl(E_(2.2)) sulfate — — — 15 C₁₂ Amine oxide 5.0 5.0 5.0 3.0 C₁₂–C₁₄Betaine 3.0 3.0 — — C₁₀ Alcohol Ethoxylate E₉ ¹ 2.0 2.0 2.0 2.0 Diamine²1.0 2.0 4.0 2.0 Mg²⁺ (as MgCl₂) 0.25 0.25 — — Ca²⁺ (as Ca(citrate)₂) —0.4 — — Polymeric suds booster³ 0.5 1.0 0.75 5.0 Minors and water⁴balance balance balance balance pH of a 10% aqueous solution 7.4 7.6 7.47.8 ¹E₉ Ethoxylated Alcohols as sold by the Shell Oil Co.²1,3-diaminopentane sold as Dytek EP. ³LX1279 available from BakerPetrolite. ⁴Includes perfumes, dyes, ethanol, etc.

Example 38

TABLE IV weight % Ingredients A B C C₁₂–C₁₃ Alkyl (E_(0.6–3)) sulfate —15.0 10.0 Paraffin sulfonate 20.0 — — Na C₁₂–C₁₃ linear alkylbenzenesulfonate 5.0 15.0 12.0 C₁₂–C₁₄ Betaine 3.0 1.0 — C₁₂–C₁₄ Polyhydroxyfatty acid amide 3.0 — 1.0 C₁₀ Alcohol Ethoxylate E₉ ¹ — — 20.0 Diamine²1.0 — 7.0 Mg²⁺ (as MgCl₂) 1.0 — — Ca²⁺ (as Ca(citrate)₂) — 0.5 —Protease³ 0.1 — — Amylase⁴ — 0.02 — Lipase⁵ — — 0.025 DTPA⁶ — 0.3 —Citrate (cit2K3) 0.65 — — Polymeric suds booster⁷ 1.5 2.2 3.0 Minors andwater⁸ balance balance balance pH of a 10% aqueous solution 9.3 8.5 11¹E₉ Ethoxylated Alcohols as sold by the Shell Oil Co.²1,3-bis(methylamino)cyclohexane. ³Suitable protease enzymes includeSavinase ®; Maxatase ®; Maxacal ®; Maxapem 15 ®; subtilisin BPN andBPN′; Protease B; Protease A; Protease D; Primase ®; Durazym ®;Opticlean ®; and Optimase ®; and Alcalase ®. ⁴Suitable amylase enzymesinclude Termamyl ®, Fungamyl ®; Duramyl ®; BAN ®, and the amylases asdescribed in WO95/26397 and in co-pending application by Novo NordiskPCT/DK/96/00056. ⁵Suitable lipase enzymes include Amano-P; M1 Lipase ®;Lipomax ®; Lipolase ®; D96L - lipolytic enzyme variant of the nativelipase derived from Humicola lanuginosa as described in U.S. patentapplication Ser. No. 08/341,826; and the Humicola lanuginosa strain DSM4106 ⁶Diethylenetriaminepentaacetate. ⁷Lysozyme. ⁸Includes perfumes,dyes, ethanol, etc.

Example 39

TABLE V weight % Ingredients A B C C₁₂–C₁₃ Alkyl (E_(0.6–3)) sulfate —27.0 — C₁₂–C₁₄ Betaine 2.0 2.0 — C₁₄ Amine oxide 2.0 5.0 7.0 C₁₂–C₁₄Polyhydroxy fatty acid amide 2.0 — — C₁₀ Alcohol Ethoxylate E₉ ¹ 1.0 —2.0 Hydrotrope — — 5.0 Diamine² 4.0 2.0 5.0 Ca²⁺ (as Ca(citrate)₂) — 0.10.1 Protease³ — 0.06 0.1 Amylase⁴ 0.005 — 0.05 Lipase⁵ — 0.05 — DTPA⁶ —0.1 0.1 Citrate (cit2K3) 0.3 — — Polymeric suds booster⁷ 0.5 0.8 2.5Minors and water⁸ balance balance balance pH of a 10% aqueous solution10 9 9.2 ¹E₉ Ethoxylated Alcohols as sold by the Shell Oil Co.²1,3-diaminopentane sold as Dytek EP. ³Suitable protease enzymes includeSavinase ®; Maxatase ®; Maxacal ®; Maxapem 15 ®; subtilisin BPN andBPN′; Protease B; Protease A; Protease D; Primase ®; Durazym ®;Opticlean ®; and Optimase ®; and Alcalase ®. ⁴Suitable amylase enzymesinclude Termamyl ®, Fungamyl ®; Duramyl ®; BAN ®, and the amylases asdescribed in WO95/26397 and in co-pending application by Novo NordiskPCT/DK/96/00056. ⁵Suitable lipase enzymes include Amano-P; M1 Lipase ®;Lipomax ®; Lipolase ®; D96L - lipolytic enzyme variant of the nativelipase derived from Humicola lanuginosa as described in U.S. patentapplication Ser. No. 08/341,826; and the Humicola lanuginosa strain DSM4106 ⁶Diethylenetriaminepentaacetate. ⁷Poly(DMAM) homolymer of Example2. ⁸Includes perfumes, dyes, ethanol, etc.

Example 40

TABLE VI weight % Ingredients A B C C₁₂–C₁₃ Alkyl (E_(1.4)) sulfate33.29 24.0 — C₁₂–C₁₃ Alkyl (E_(0.6)) sulfate — — 26.26 C₁₂–C₁₄Polyhydroxy fatty acid amide 4.2 3.0 1.37 C₁₄ Amine oxide 4.8 2.0 1.73C₁₁ Alcohol Ethoxylate E₉ ¹ 1.0 4.0 4.56 C₁₂–C₁₄ Betaine — 2.0 1.73MgCl₂ 0.72 0.47 0.46 Calcium citrate 0.35 — — Polymeric suds booster²0.5 1.0 2.0 Minors and water³ balance balance balance pH of a 10%aqueous solution 7.4 7.8 7.8 ¹E₉ Ethoxylated Alcohols as sold by theShell Oil Co. ²Dimethylaminoethyl methacrylate/dimethylacrylamidecopolymer according to any one of Examples 1. ³Includes perfumes, dyes,ethanol, etc.

Example 41

A B C D E AE0.6S¹ 28.80 28.80 26.09 26.09 26.09 Amine oxide² 7.20 7.206.50 6.50 6.50 Citric acid 3.00 — — — — Maleic acid — 2.50 — — — Sudsboosting 0.22 0.22 0.20 0.20 0.20 polymer³ Sodium 3.30 3.30 3.50 3.503.50 Cumene Sulfonate Ethanol 40B 6.50 6.50 6.50 6.50 6.50 C10E8 — —3.00 3.00 3.00 C11E9⁴ 3.33 3.33 — — — Diamine⁵ 0.55 0.55 0.50 0.50 0.50Perfume 0.31 0.31 — — — Water BAL. BAL. BAL. BAL. BAL. Viscosity (cps330 330 150 330 650 @ 70 F.) pH @ 10% 9.0 9.0 8.3 9.0 9.0 F G H I JAE0.6S¹ 26 26 26 26 26 Amine oxide² 6.5 6.5 7.5 7.5 7.5 Citric acid 3.0— 2.5 — 3.0 Maleic acid — 2.5 — 3.0 — C10E8⁶ 3 3 4.5 4.5 4.5 Diamine⁵0.5 0.5 1.25 0 1.25 Diamine⁷ 0 0 0 1 Suds boosting 0 0.2 0.5 0.5 0.5polymer³ Sodium cumene 3.5 3.5 2 2 2 sulphonate Ethanol 8 8 8 8 8 pH 9 99 8 10 ¹C12–13 alkyl ethoxy sulfonate containing an average of 0.6ethoxy groups. ²C₁₂–C₁₄ Amine oxide. ³Polymer is(N,N-dimethylamino)ethyl methacrylate homopolymer ⁴C11 Alkyl ethoxylatedsurfactant containing 9 ethoxy groups. ⁵1,3bis(methylamine)-cyclohexane. ⁶C10 Alkyl ethoxylated surfactantcontaining 8 ethoxy groups. ⁷1,3 pentane diamine.

Example 42

Skin feel is determined by the modified acid phosphatase, or MAP method.

-   This method describes a rapid screening enzyme assay which predicts    skin mildness of surfactant systems by measuring acid phosphatase    inhibition as a result of exposure to surfactants.    Procedure

Equipment

-   -   96 well flat bottom microtiter plate,    -   Finnipipette (Labsystems) digital multichannel pipette (50–300        ul) with reservoir and tips,    -   Eppendorf repeater pipette with tips (1.25 and 5 ml),    -   gloves    -   plate shaker    -   plate reader (EL312 microplate by Bio Tek Instruments—Bio        Kinetics Reader)    -   microtiter plate heating block    -   pH meter    -   Gilson pipetman pipettes (10–100 ul; 100–1000 ul) with tips

Reagents

-   -   purified acid phosphatase (typically, potato, type II        lyophilized, from Sigma, P3752)    -   Disodium p-nitrophenylphosphate (typically, Sigma 104        phosphatase substrate)    -   citric acid (reagent grade)    -   sodium citrate (reagent grade)    -   HPLC grade water (or distilled/deionized/high quality water        (HQW))    -   water hardness concentrate (3:1 Ca++/Mg++, ITC supply)    -   Sodium hydroxide (0.5N NaOH)    -   Predried porcine stratum corneum

Preparation of Solutions:

-   -   Prepare enzyme solution by making a 1–2 mg/ml solution (to give        O.D. at 405 nm of 1.2–1.7 with a target of 1.5) of purified acid        phosphatase (0.5–1.0 units of activity/mg at room temperature)        in HPLC water and keep on ice. Make fresh prior to use.    -   Prepare citrate buffer at pH4.5 by combining 0.82 g citric acid,        2.25 g sodium citrate, and Q.S. to 100 ml with HPLC water.    -   Prepare substrate/buffer solution: 3.0 mM        p-nitrophenylphosphatase (F.W.263) in 10 mM citrate buffer@pH        4.5 (add 8 mg PNPP in 10 ml citrate buffer.    -   Prepare development solution: 0.5N NaOH.    -   Make 7 gpg water: Add 0.6 ml of hardness concentrate to 1000 ml        of HPLC water

Partitioning Followed by Extraction of Surfactants into Stratum Corneum

-   -   Place the surfactant solution (300 g) at the desired water        hardness in a 115F waterbath to get to temperature.    -   Cut and weigh the predried porcine stratum corneum to get        approximately the same size by weight sample from the same piece        of pigskin for the treatments to be tested and compared.    -   Place the pigskins in the appropriate solutions, making sure the        pigskins stay at the bottom of beaker to insure all surface is        exposed to solution, and let soak for 30 minutes at the 115 F        temperature.    -   After the soak, the pigskin is rinsed (or placed) in fresh room        temperature 0 gpg water for 30 seconds.    -   After the rinse the pigskin is placed in a clean 15 ml vial and        HQW (12–14 ml) is added to the vial and aluminum foil is placed        on the top of vial before lid is screwed on.    -   The vial is placed in the 115 F waterbath for 2 hours and during        the 2 hours inverted every ½ hr.    -   After the extraction for 2 hrs the pigskin is removed and        discarded and the extract is evaporated to dryness using dry        N2(overnight drying).    -   Reconstitute the dried extract with 0.4 ml HQW and place back        into waterbath set at 50–55 C to insure surfactant goes in        solution—the solution should be clear.

Addition of Surfactants to Microtiter Wells

-   -   Place empty microtiter plate on pre-heated plate warming block        (115F). Place thermometer in plate and wait for temperature to        reach @ 113 F.    -   Add 50 ul of the heated extracted surfactant solutions (400 ul)        to designated wells. Add 50 ul of 115 F water (hardness in which        soak was conducted) to control wells and the blanks. Generally,        blanks are run as the first well in each row. (see Appendix II        for template setup)    -   Add 25 ul of the enzyme solution to each well except blanks (the        control will have enzyme, but no surfactant, and will show the        highest enzyme activity) as quickly as possible (<30 sec.). Add        25 ul of the 115 F water (hardness in which soak was conducted)        to the blanks. Once enzyme added to first well set timer for        five minutes.    -   Move microtiter plate to plate shaker. Shake for 30 seconds.    -   Return microtiter plate to plate warming block for the duration        of the five minutes. After the five minutes remove from heating        block.    -   Add 75 ul of the substrate/buffer solution to each well using        the multi-channel pipette. This step activates the enzyme to        liberate product, so the solution must be added as quickly and        as accurately as possible (<30 sec.). Activate wells of a single        row first before adding solution to wells of the next row.    -   After 3 minutes, quickly add 100 ul of 0.5N NaOH to each well        using the multi-channel pipette. This step stops the reaction        and develops the color for the spectrophotometric measurement at        405 nm using the plate reader, so this solution must also be        added as quickly and as accurately as possible (<30 sec.). The        color will be stable for up to 30 minutes if the plate is        covered.    -   Obtain absorbance results using plate reader set at 405 nm.

Background Correction

-   -   Some surfactants may interfere at 405 nm and background        correction is required for these materials. The correction is        made by simply redoing the above 8 steps with the exception of        adding the enzyme solution. This is replaced with 25 ul of        water. Read wells at 405 nm and subtract background absorbance        values from absorbances (average) derived from corresponding        reacted wells. A background subtraction should be performed for        every surfactant and product tested.

Calculation

-   -   Subtract blank absorbance value from control absorbance value to        obtain the absorbance of the control wells (maximum enzyme        introduced in the experiment). Subtract surfactant absorbance        backgrounds from appropriate surfactant—acid phosphatase        absorbances to obtain absorbance of surfactant wells.    -   Derive Ratio of Inhibition (or % enzyme deactivation) for each        concentration as follows:        [1−(absorbance of surfactant/absorbance of control)]*100

Reporting

-   -   Report the % enzyme deactivation of the different formulae        tested and compare to a control product. An increase in %        deactivation corresponds to greater product harshness outside        the standard deviation of test method (+/−4%).        Effect of Including Polymeric Suds Booster in an LDL Composition

The LDL composition tested has the formula

AE0.6S 26.6 Amine Oxide 6.60 C11E9/C10E8 3.1 Diamine 0.5 Polymer 0.22water minors qs to 100%

The polymer used is the polymer of Example 2 above. MAP results are in %deactivation

Hardness, in LDL with grains per 0.22% LDL with nil- gallon polymerpolmer 2 gpg 27B 46 7 gpg 37BC 50

This result clearly shows the mildness benefit gained from including thesuds boosting polymers of the present invention.

1. A composition for manually cleaning an object, said compositioncomprising a hand laundry composition, a personal cleansing composition,or a shampoo, in which suds produced by the composition in an aqueouswashing solution is maintained for an extended period of time by apolymeric suds stabilizer, said suds stabilizer being selected from thegroup consisting of: (a) polymers comprising at least one monomeric unitof the formula:

 wherein each of R¹, R² and R³ are independently selected from the groupconsisting of hydrogen, C₁ to C₆ alkyl, and mixtures thereof; L isselected from the group consisting of O, NR⁶, SR⁷R⁸ and mixturesthereof, wherein R⁶ is selected from the group consisting of hydrogen,C₁ to C₈ alkyl and mixtures thereof; each of R⁷ and R⁸ are independentlyhydrogen, O, C₁ to C₈ alkyl and mixtures thereof, or SR⁷R⁸ form aheterocyclic ring containing from 4 to 7 carbon atoms, optionallycontaining additional hetero atoms and optionally substituted; Z isselected from the group consisting of: —(CH₂)—, (CH₂—CH═CH)—,—(CH₂—CHOH)—, (CH₂—CHNR⁶)—, —(CH₂—CHR¹⁴—O—)— and mixtures thereof;wherein R¹⁴ is selected from the group consisting of hydrogen, C, to C₆alkyl and mixtures thereof; z is an integer selected from 0 to 12; A isNR⁴R⁵, wherein each of R⁴ and R⁵ are independently selected from thegroup consisting of hydrogen, C₁ to C₈ alkyl, and mixtures thereof, orNR⁴R⁵ form an heterocyclic ring containing from 4 to 7 carbon atoms,optionally containing additional hetero atoms, optionally fused to abenzene ring, and optionally substituted by C₁ to C₈ hydrocarbyl; andwherein said polymeric suds stabilizer has a molecular weight of from1,000 to 2,000,000 daltons; (b) a proteinaceous suds stabilizer, saidproteinaceous suds stabilizer having an isoelectric point of from 7.5 to11.5; (c) a zwitterionic polymeric suds stabilizer; and (d) mixturesthereof; wherein said composition further comprises an organic diaminehaving a molecular weight less than or equal to 400 g/mol.
 2. Thecomposition according to claim 1, wherein said polymeric suds stabilizerhas a molecular weight of from 5,000 to 1,000,000.
 3. The compositionaccording to claim 1, wherein said zwitterionic polymeric sudsstabilizer has the formula:

wherein R is C₁–C₁₂ linear alkylene, C₁–C₁₂ branched alkylene, andmixtures thereof; R¹ is a unit capable of having a negative charge at apH of from 4 to 12; R² is a unit capable of having a positive charge ata pH of from 4 to 12; n has a value such that said zwitterionic polymerssuds stabilizer has an average molecular weight of from 1,000 to2,000,000 daltons; x is from 0 to 6; y is 0 or 1; and z is 0 or
 1. 4.The composition according to claim 1, wherein the proteinaceous sudsstabilizer comprises at least about 10% by weight of one or more aminoacids which are protonated at a pH of less than about
 11. 5. Thecomposition according to claim 1, wherein said polymeric suds stabilizerfurther comprises: i) units capable of having an anionic charge at a pHof from 4 to 12; ii) units capable of having an anionic charge and acationic charge at a pH of from 4 to 12; iii) units having no charge ata pH of from 4 to 12; or iv) mixtures thereof.
 6. The compositionaccording to claim 1, wherein said polymeric suds stabilizer is selectedfrom the group consisting of a homopolymer, a copolymer and aterpolymer.
 7. The composition according to claim 1, wherein saidcomposition further comprises a detersive surfactant selected from thegroup consisting of anionic surfactant, nonionic surfactant, amphotericsurfactant, zwitterionic surfactant, cationic surfactant, and mixturesthereof.
 8. The composition according to claim 7, wherein said detersivesurfactant is an anionic surfactant selected from the group consistingof C₈–C₁₈ alkyl benzene sulfonates, C₈–C₁₈ alkyl sulfates containingfrom 0 to 3 ethenoxy groups in the molecule, C₈–C₂₅ olefin sulfonates,C₁₀–C₂₀ paraffin sulfonates, C₈–C₉ alkyl phenol ethoxamer sulfates, andmixtures thereof.
 9. The composition according to claim 1, wherein saiddiamine is selected from the group consisting of dimethyl aminopropylamine, 1,6-hexane diamine, 1,3 propane diamine, 2-methyl 1,5 pentanediamine, 1,3-pentanediamine, 1,3-diaminobutane,1,2-bis(2-aminoethoxy)ethane, isophorone diamine,1,3-bis(methylamine)-cyclohexane and mixtures thereof.
 10. Thecomposition according to claim 1, wherein said composition furthercomprises an anionic surfactant, an amine oxide, and an enzyme, whereinsaid enzyme is selected from the group consisting of amylase, proteaseand mixtures thereof.
 11. The composition according to claim 10, whereinsaid composition further comprises an effective amount of magnesiumions.
 12. The composition according to claim 1, wherein said compositionis selected from the group consisting of granules, tablets, liquids,liqui-gels, gels, microemulsion, thixatropic liquid, bars, pastes,powders and mixtures thereof.
 13. The composition according to claim 1,wherein said composition substantially reduces skin irritation of thehands by said detergent composition.
 14. A composition for cleaning theskin while avoiding the harsh effects on the skin of an anionicsurfactant said composition comprising an anionic surfactant and apolymeric suds stabilizer selected from the group consisting of: (a)2-(dimethylamino)ethyl methacrylate homopolymer, 2-(dimethylamino)ethylmethacrylate/dimethylacrylamide copolymer and 2-(dimethylamino)ethylmethacrylate/acrylic acid copolymer; wherein said polymeric sudsstabilizer has a molecular weight of from 1,000 to 2,000,000 daltons;(b) a proteinaceous suds stabilizer, said proteinaceous suds stabilizerhaving an isoelectric point of from 7.5 to 11.5; (c) a zwitterionicpolymeric suds stabilizer; and (d) mixtures thereof; said compositionfurther comprising an organic diamine having a molecular weight lessthan or equal to 400 g/mol.
 15. The composition according to claim 14,wherein said composition further comprises a detersive surfactantselected from the group consisting of nonionic surfactant, amphotericsurfactant, zwitterionic surfactant, cationic surfactant, and mixturesthereof.
 16. The composition according to claim 14, wherein said anionicsurfactant is selected from the group consisting of C8–C₁₋₈ alkylbenzene sulfonates, C₈–C₁₈ alkyl sulfates containing from 0 to 3ethenoxy groups in the molecule, C₈–C₂₅ olefin sulfonates, C₁₀–C₂₀paraffin sulfonates, C₈–C₉ alkyl phenol ethoxamer sulfates, and mixturesthereof.
 17. The composition according to claim 14, wherein said diamineis selected from the group consisting of dimethyl aminopropyl amine,1,6-hexane diamine, 1,3 propane diamine, 2-methyl 1,5 pentane diamine,1,3-pentanediamine, 1,3-diaminobutane, 1,2-bis(2-aminoethoxy)ethane,isophorone diamine, 1,3-bis(methylamine)-cyclohexane and mixturesthereof.